CN104492284B - A kind of two-sided dissymmetrical structure flat support film and its preparation method and application - Google Patents
A kind of two-sided dissymmetrical structure flat support film and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of two-sided dissymmetrical structure flat support film and its preparation method and application, belong to membrane separation technique and field of new materials.A kind of preparation method of two-sided dissymmetrical structure flat support film, supporter is set along the direction parallel with gravity direction, and two surfaces of supporter is contacted casting solution, the supporter contacted after casting solution is handled in coagulation bath, wherein, the casting solution, by mass percentage, is made up of following components：10%~30% polymer, 3%~20% additive, surplus organic solvent；The viscosity of casting solution is 2000~102000mPas.The two-sided asymmetric flat support film that the present invention is provided has the performances such as higher mechanical strength, homogeneous fine and close pore structure, good solvent resistant, acid and alkali-resistance, contaminative, easy cleaning, is more suitable for applying and contains solvent, strong acid aqueous slkali and sewage system in the fine separation fields such as nanofiltration, counter-infiltration, gas separation and processing.
Description
Technical field
The present invention relates to a kind of two-sided dissymmetrical structure flat support film and its preparation method and application, belong to UF membrane skill
Art and field of new materials.
Background technology
Membrane separation technique is a kind of new isolation technics, compared with conventional separation techniques, and the advantage of UF membrane is height
Effect energy-conservation, process be simple and convenient to operate, environment-friendly, and is easy to and other technologies are integrated couples.Membrane material is UF membrane skill
The core of art, according to the difference of shape, film can be divided into several forms such as flat, tubular type, rolling, doughnut.Wherein, put down
The flux of plate film is higher, and preparation technology is simple, and separation condition is easily controllable, and mechanical strength is higher, and the life-span is longer, therefore poly- by height
Plate porous membrane material prepared by thing is accounted in the membrane separating process such as micro-filtration, ultrafiltration, nanofiltration, counter-infiltration and gas isolation of purified
According to leading position.The preparation method of current flat board apertured polymeric film includes inversion of phases, fusion drawn method, etching method etc., wherein
Immersion precipitation phase inversion process is one of film-forming method for being most widely used.
Traditional dissymmetrical structure flat support membrane preparation method generally uses immersion precipitation phase inversion process, including knife coating
With spraying process etc..Its preparation process is by polymeric casting film liquid to scratch or be sprayed on supporter non-woven fabrics using traditional knifing machine
Surface on, be then immersed in coagulation bath i.e. non-solvent, occur inversion of phases form asymmetric flat support film.Chinese patent Shen
Please number be CN200510060289.7, publication date be on 2 8th, 2006, the entitled " preparation of co-mixed polyethersulfone platform complex film
Method " is disclosed using traditional knifing machine continuous striking polyether sulfone and sulfonated polyether sulfone blend film on supporting layer, is subsequently dipped to
Flat composite membrane is formed into coagulation bath.Chinese Patent Application No. is CN200910228659.1, and publication date is June 9 in 2010
Day, entitled " preparation method of temperature response type polyvinylidene fluoride flat separation film " is disclosed using temperature sensitive copolymer as casting solution,
Using glass bar striking film forming on a glass, freezing film in constant temperature coagulation bath is subsequently dipped to.Chinese Patent Application No. is
CN201310249374.2, publication date is September in 2013 4, a kind of entitled " preparation of hydrophilic polyvinylidene fluoride flat sheet membrane
Method ", which is disclosed, is coated to Kynoar casting solution on non-woven fabrics base material using classic flat-plate knifing machine, then will be entered
Gel film forming in coagulation bath, and carried out hydrophilically modified.Chinese Patent Application No. is 201310563801.X, and publication date is
On April 3rd, 2013, entitled " a kind of preparation method of polymer flat plate microporous barrier ", which is disclosed, utilizes pneumatic spray gun by casting solution
Round repetition is sprayed on flat plate mold, and the mould for being coated with casting solution then is put into gel film forming, etc. in coagulation bath.
Flat support film prepared by the method provided using above-mentioned patent, because casting solution is coated in supporting body surface,
The film layer structure formed after inversion of phases is usually the one side dissymmetrical structure with macropore, transitional pore and surface dense layer, and
Supporter is generally nonwoven cloth material, and its service life and solvent resistant, heat resistance and resistance to strong acid, strong basicity are poor.So, it is this flat
Not only fault of construction is more for plate support membrane, while in application because body nature supported is limited, it is impossible to used wider,
Such as containing solvent, the solution of strong acid-base and sewage system to some can not be used for a long time.
The content of the invention
It is an object of the invention to overcome the shortcomings of that there is provided a kind of two-sided dissymmetrical structure in prior art and membrane structure
The preparation method of flat support film.To achieve these goals, the present invention uses following technical scheme：
A kind of preparation method of two-sided dissymmetrical structure flat support film, by the supporter edge direction parallel with gravity direction
Set, and two surfaces of supporter is contacted casting solution, the supporter contacted after casting solution is handled in coagulation bath,
Wherein, the casting solution, by mass percentage, is made up of following components：10%~30% polymer, 3%~
20% additive, surplus organic solvent；The viscosity of casting solution is 2000~102000mPas；
The polymer be polyimides, polyacrylonitrile, polysulfones, polyether sulfone, polyethersulfone ketone, polyethers eyeball ketone, PAEK,
Polytetrafluoroethylene (PTFE), Kynoar or cellulose acetate；
The additive is polyethylene glycol, polyvinylpyrrolidone, water, glycerine, butanol, ethylene glycol, acetone, chlorination
One or more in lithium, zeolite molecular sieve, nano silicon, titanium oxide, graphene, carbon nanotube.
The preparation method of two-sided dissymmetrical structure flat support film of the present invention is that supporter edge is parallel with gravity
Direction is set or mobile, and carries out film forming using film formation device, and the film formation device includes two relative film forming faces and film forming face
It is parallel with supporter plane so that two surfaces of the supporter between two film forming faces contact casting solution, obtain two-sided
Coat the supporter of casting solution.Spacing between preferably two film forming faces of the invention is 100~600 μm.
The preparation method of two-sided dissymmetrical structure flat support film of the present invention, the viscosity of the casting solution is preferably
4000~62000mPas.
The preparation method of two-sided dissymmetrical structure flat support film of the present invention, the organic solvent adds for that can dissolve
Plus the available organic solvent of agent and polymer, and so that finally the viscosity of gained casting solution is of the invention in the range of requiring
It is preferred that the organic solvent is that DMA, DMF, 1-METHYLPYRROLIDONE or dimethyl are sub-
Sulfone.
The preparation method of two-sided dissymmetrical structure flat support film of the present invention, the supporter is with uniform netted
The supporter of structure, mesh size is 10~200 μm.It is disclosed available for not that supporter of the present invention can select prior art
The supporter of symmetric support film preparation, the present invention preferably polymeric web, stainless (steel) wire, titanium net or copper mesh, the polymeric web,
Polymer can be nylon wire, polythene net, polypropylene net, ABS nets or polyester webs.
The preparation method of two-sided dissymmetrical structure flat support film of the present invention, preferably contact of the supporter with casting solution
Time is 10~30min.
The preparation method of two-sided dissymmetrical structure flat support film of the present invention, the branch that will preferably have been contacted with casting solution
Support body is handled in two coagulation baths successively.The coagulation bath includes the first coagulation bath and the second coagulation bath, described first
Coagulation bath, by mass percentage, is made up of following components：0%~50% organic solvent and excess water, wherein, organic solvent is
DMA, DMF, chloroform, 1-METHYLPYRROLIDONE or dimethyl sulfoxide (DMSO)；Described second coagulates
Glue bath is water.
Further, it is preferable to which the processing time in the first coagulation bath is 30s~20min；Place in the second coagulation bath
The reason time is 3~48h.
The preparation method of two-sided dissymmetrical structure flat support film of the present invention, preferably makes the branch after being contacted with casting solution
Support body stops 10s~20min before coagulation bath is entered in air.
The preparation method of two-sided dissymmetrical structure flat support film of the present invention, a preferred technical scheme is：
Supporter is set along the direction parallel with gravity direction, and two surfaces of supporter is contacted casting solution,
Casting solution is set to contact 10~30min with supporter；The supported liquid membrane after contact is set to stop 10s~20min in atmosphere；Then enter
Enter in the first coagulation bath, stop 30s~20min；Subsequently into the second coagulation bath, 3~48h is stopped.
The preferably two-sided dissymmetrical structure flat support film of the invention is prepared in following apparatus.
A kind of process units of flat support film, described device includes：
Film forming mechanism, the film forming mechanism includes film forming room；Film-forming plates group in film forming room, the film-forming plates group by
Two film forming face relative film-forming plates composition directly, are faced directly by film forming and set the film-forming plates parallel to gravity direction；Control device,
For controlling at least two one-tenth templates in film-forming plates group to be moved up in the side perpendicular to gravity direction；
Impregnating mechanism, impregnating mechanism includes the container that at least one takes up coagulation bath；The impregnating mechanism is received and come from into
The supporter of film mechanism, and make in the bath of supporter immersion precipitation；
Transport mechanism, the transport mechanism makes supporter enter film forming mechanism along the direction parallel with gravity direction, and will
Supporter by film forming mechanism sends into impregnating mechanism and supporter is stopped certain time in coagulation bath.
In above-mentioned technical proposal, each film-forming plates group include two identicals, film forming faces be oppositely arranged into template,
The film forming face is to be hoped the face of film forming thereon；The film forming face of single film-forming plates to face directly, and the film forming face directly parallel to
Gravity direction.Film-forming plates described in above-mentioned technical proposal make film forming liquid produce gravity flow using gravity, and then on film forming is faced directly
Film forming.
In above-mentioned technical proposal, the control device is used to control at least one film-forming plates in film-forming plates group.The control
Device processed can only control into that template group two is mobile into one of template, so change two film forming face directly between distance；The control
Device processed can also control into two in template group simultaneously into template movement, make two film-forming plates film forming face directly towards or away from
It is mobile, change two film forming face directly between distance, and then reach the purpose of control film forming thickness.
Film forming mechanism of the present invention is preferably described to be included film forming into template and faces and faced directly with film forming being used for of being connected directly
Film forming raw material liquid is set to flow to the guide face that film forming is faced directly.
Film forming mechanism of the present invention further comprise for so that film forming raw material smoothly and uniformly flow to what film forming was faced directly
Guide face, the guide face can be to face directly or curved surface, be preferably and face directly；The film forming is faced directly can be integrated with guide face
Structure, also can be assembled gained.
The preferably film forming into template of the invention is faced directly is mutually angle connection with guide face.When guide face is to face directly,
The film forming into template is faced directly generally forms a folding face with guide face.Faced directly when film forming has certain angle between guide face
When, two film-forming plates match to form the shape of funnel, are easy to the gravity flow of film forming liquid.
The preferably guide face of the invention is faces directly, and the film forming faces the angle α between guide face directly for 0~90 ° (no
Including 90 °), preferably 30~60 °, more preferably 45~60 °.Of the present invention and number range, unless otherwise indicated,
It includes endpoint value in itself.
The film forming mechanism of the present invention preferably control device includes：Power set and use cooperatively with power set
Transmission device, the transmission device includes：
At least two groups guide rails, the guide rail is set by parallel into the direction of template movement；
The sliding block used cooperatively with guide rail, the sliding block is fixed on into template；
Lead screw gear, the lead screw gear includes the leading screw being connected with power set and with mutually being fixed into template
Feed screw nut, and the leading screw is set by parallel into the direction of template movement.
Preferably one film-forming plates of above-mentioned technical proposal are used cooperatively with least two lead screw gear.
In above-mentioned technical proposal, the guide rail is securable to the top of film forming room, and by parallel into the side of template movement
To the above-mentioned guide rail of setting；The transmission device at least includes two groups of guide rails, and two groups of guide rails are respectively placed in into the edge side of template,
To ensure into the steady movement of template.
Power set of the present invention are the device that this area is used to provide power, such as motor.
In above-mentioned technical proposal, to ensure multiple lead screw gear synchronous operations, it is synchronous that described device also includes motor
Control device, such as motor isochronous controller, motor drum in-phase.
To prevent leading screw causes into template to the support force deficiency into template from producing larger deformation, make the film to be formed uneven
It is even, support film-forming plates using multiple leading screws；During one leading screw action, in order that all leading screws of film-forming plates side are acted simultaneously,
The synchronizing wheel installed on active leading screw, the synchronizing wheel being installed on adjacent leading screw is driven by timing belt, and then drive adjacent
The motion of leading screw, it is ensured that the motion of roomy film-forming plates.
Further, described leading screw one end passes through the fixed plate and connecting power device for being fixed on film forming room's side wall, another
End is through feed screw nut, and the feed screw nut is fixed on into template by connector.
Film forming mechanism of the present invention is preferably described to include fixed part, the sliding block and the fixed part phase into template into template
It is fixed.
In above-mentioned technical proposal, the position that the fixed part is set is determined according to the position of guide rail so that disposed thereon
Sliding block and guide rail can match use.
It can be fixed between all parts of the present invention using mode disclosed in prior art, such as utilize pin, key, bolt
Deng.
Film forming mechanism of the present invention preferably includes the space for storing into film liquid.
Film forming mechanism of the present invention preferably includes heater, and the heater can keep what is deposited in film forming mechanism
Into film liquid within the temperature range of setting.
Impregnating mechanism of the present invention may include one or more containers for taking up coagulation bath.When impregnating mechanism is including multiple
During container, each container can be used for taking up the identical or different coagulation bath of component.
When impregnating mechanism takes up the container of coagulation bath including one, supporter is in film forming mechanism with fully being connect into film liquid
After touch, moved down along gravity direction, vertically into coagulation bath, and communicated mechanism causes the support into coagulation bath
Body stops the time of setting in coagulation bath.
When impregnating mechanism include it is multiple take up the container of coagulation bath when, supporter is in film forming mechanism with fully being connect into film liquid
After touch, moved down along gravity direction, vertically into first coagulation bath, and communicated mechanism to enter first gel
The supporter of bath stops the time of setting in first coagulation bath；Then by transport mechanism by by the support of first coagulation bath
Body is sequentially sent to other coagulation baths and stopped the time each set.
The time of above-mentioned setting can by take up coagulation bath container size and control transmission mechanism transmission speed
Reach.
Transport mechanism described in device of the present invention includes transfer roller groups and tension control system.
Tension control system of the present invention is commercially available, or method is made according to disclosed in prior art, and it is selected
And be set to the state of the art, those skilled in the art can be carried out by method disclosed in prior art selection and
Set.
Transfer roller groups of the present invention are made up of multiple rollers, and the plurality of roller send the supporter being wound on let off roll successively
Enter film forming mechanism and impregnating mechanism, the support film income wind-up roll for finally obtaining reaction.
Further, the transfer roller groups include：
Let off roll and wind-up roll；
Receive the tension sensor carrying roller of the supporter from let off roll；
The pretension for receiving the supporter from sensor carrying roller is tested to roller；
Receive and test slewing rollers to the supporter of roller from pretension, by the slewing rollers supporter along gravity direction to
Lower movement simultaneously enters film forming mechanism；
The slewing rollers I being located in coagulation bath of the supporter from film forming mechanism is received, the supporter by slewing rollers I exists
Move, and moved up after diverted roller II along gravity direction in the horizontal direction in coagulation bath, supporter is wound to winding
On roller.
In above-mentioned technical proposal, the tension control system is preferably set in the following manner：The pretension test is in roller
Pretension test lower roll roller one end connection encoder, rotating cycle and discharge uneven in supporter motion process based on
Tension force, improves supporter flatness and Tension Evenness.Magnetic tension controller is connected on let off roll, tension sensor carrying roller
It is provided with tension sensor；Magnetic tension controller receive tension sensor feedback signal on tension sensor carrying roller with
And the tension force of operating personnel's setting controls pre-tightening tension, setting numerical value is generally 0~0.2A.
Transfer roller groups of the present invention may also include some transition rollers.
Device of the present invention also includes power set and control device, the translational speed for controlling supporter.Work as biography
When sending mechanism for transfer roller groups, device preferably of the present invention includes some motors and control device, for controlling each roller
Operation.
It is a further object of the present invention to provide the two-sided dissymmetrical structure flat support film prepared by the above method.
The support membrane be by dense layer surface, transition zone, macroporous layer, transition zone, dense layer surface constitute successively it is two-sided not right
Claim layer.
It is yet another object of the invention to provide a kind of carbon membrane and preparation method thereof.
A kind of preparation method of carbon membrane, is that two-sided dissymmetrical structure flat support film is placed in retort, in indifferent gas
Carbonized under atmosphere.
In the preparation method of above-mentioned carbon membrane, preferably carbonization temperature is 600~800 DEG C；It is preferred that carbonization time is at least 2h.
It is yet another object of the invention to provide rigid seperation film of a kind of thermic and preparation method thereof.
A kind of thermic rigidly separates the preparation method of seperation film, is that two-sided dissymmetrical structure flat support film is placed in into heating
In stove, nitrogen or air are passed through with 300mL/min flow velocity into stove, furnace temperature is warming up to 200~450 with 5 DEG C/min speed
DEG C, and constant temperature is after at least 1 hour, Temperature fall, obtains the rigid seperation film of thermic.
Beneficial effects of the present invention are：The flat support film prepared using the present invention has two-sided dissymmetrical structure：Casting film
In surface, hole or gap of the liquid full of porous supporting body, polymer film and the supporter of formation are combined closely, and are combined together；
Polymer film axle centered on supporter, forms pair being made up of dense layer surface, transition zone, macroporous layer, transition zone, dense layer surface
Face dissymmetrical structure film layer, and pore structure forms interpenetrating structure on supporter.
Compared with the Flat Membrane that traditional immersion precipitation phase inversion process is prepared, the two-sided asymmetric flat board branch that the present invention is provided
Supportting film has higher mechanical strength, homogeneous fine and close pore structure, good solvent resistant, acid and alkali-resistance, contaminative, easy cleaning etc.
Performance, is more suitable for applying and contains solvent, strong acid aqueous slkali in the fine separation fields such as nanofiltration, counter-infiltration, gas separation and processing
And sewage system.In addition it is high, suitable continuous that preparation method of the invention is simple to operation, stability is good, technique can adjust degree
Production.
In addition, two-sided dissymmetrical structure flat support film prepared by the present invention has good heat endurance, heat through heat
Self-crosslinking rearrangement reaction or oxidation heat cross-linking rearrangement reaction is caused to form the crosslinking seperation film with rigid stable construct, in inertia
Under atmosphere, through high temperature carbonization, high osmosis, high separation selectivity carbon membrane can be prepared.
Brief description of the drawings
Fig. 1 is a kind of process units of flat support film,
Reference is as follows：
1a, slewing rollers I, 1b, slewing rollers II, 2a, transition roller I, 2b, transition roller II, 3, gel bath, 4, coagulation bath, 5,
Wind-up roll, 6, let off roll, 7, tension sensor carrying roller, 8, pretension test the speed upper roller, 9, pretension test the speed lower roll, 10, transition roller, 11,
Slewing rollers, 12, film forming mechanism, 13, film-forming machine constitute film unit, 14, supporter；
Fig. 2 is a kind of schematic diagram of film forming mechanism,
Fig. 3 is a kind of schematic side view of film forming mechanism,
Reference is as follows：
101st, motor, 200, side wall, 300, fixed plate, 400, into template, 401, film forming face directly, 402, guide face, 500,
Guide rail, 600, sliding block, 700, connector, 800, feed screw nut, 900, leading screw.
Fig. 4 (a) and (b) are the gained of embodiment 1 two-sided dissymmetrical structure flat support film section electromicroscopic photograph；Wherein, Fig. 4
(a) be support membrane first half section electromicroscopic photograph, it can be seen that gained support membrane from top to bottom for dense layer surface,
Transition zone and macroporous layer；Fig. 4 (b) be support membrane lower half section electromicroscopic photograph, it can be seen that gained support membrane by
Up to lower is macroporous layer, transition zone and dense layer surface.
Fig. 5 is the photo of two-sided dissymmetrical structure flat support film obtained by (a) and (b), as can be seen that gained from photo
Support membrane is smooth, smooth, uniform, pin-free and defect.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
It is mass percent wt% to be related to percentage % in following embodiments.Tension controller used in following embodiments
For GXFZ-B-6 type electromagnetic power brakes, artificial setting numerical value is generally 0~0.2A；Tension sensor model：CZH-25
Type tension sensor；The number of turns and Production rate are used：E6B2-CWZ6C type encoders.
Used film forming device is as shown in Figures 1 to 3 in following embodiments.
As shown in figure 1, a kind of process units of flat support film, described device includes：Film forming mechanism, impregnating mechanism and biography
Send mechanism.
The film forming mechanism is as shown in Fig. 2 the film forming mechanism includes Liang Ge film forming room side wall 200, two fixed plates
300th, two film-forming plates 400, two guide rails 500, four sliding blocks 600, four leading screws 900, four feed screw nuts 800, four silks
Thick stick screw connector 700, two groups of motor drum in-phases 110, two timing belts 120, two motors 101, and connect above-mentioned zero
Screw, bolt, nut, key, the pin of part.
The film-forming plates 400 face 401 and guide face 402 directly including film forming, the guide face 402 to face directly, and it is described into
The angle that film faces between 401 and guide face 402 directly is 30 °.401 are faced directly parallel to the gravity direction setting film-forming plates by film forming
400。
Fixed plate 300 is fixed between Liang Ge film forming room side wall 200, and the spacing between Liang Ge film forming room side wall 200 is by two
The length of fixed plate 300 is determined.Two guide rails 500 are separately mounted on Liang Ge film forming room side wall 200, by parallel to film-forming plates
The direction of 400 movements sets the guide rail 500；Four sliding blocks 600 are separately mounted to the top of two film-forming plates 400, and it is set
Position causes sliding block 600 to be moved on guide rail 500.Two feed screw nut connectors 700 are fixed on each film-forming plates 400, are connected
Feed screw nut 800 is fixed on fitting 700, one end of one of leading screw 900 passes through feed screw nut 800, and the other end, which is passed through, to be fixed
Plate 300 is simultaneously connected with motor 101, and synchronizing wheel 100 is housed on leading screw 900；One end of another leading screw 900 passes through feed screw nut
800, the other end, which passes through to be equipped between another synchronizing wheel 110, two synchronizing wheels 110 on fixed plate 300, leading screw 900, is provided with timing belt
120。
The impregnating mechanism, impregnating mechanism includes a gel bath 3 for taking up gel；The impregnating mechanism is received and come from
The supporter 14 of film forming mechanism, and supporter is immersed in 14 coagulation baths 4.
The transport mechanism includes transfer roller groups and tension control system, and the transfer roller groups include：Let off roll 6 and winding
Roller 5；Receive the tension sensor carrying roller 7 of the supporter 14 from let off roll 6；Receive the supporter 14 from sensor carrying roller 7
Pretension test to roller, pretension test includes that pretension tests upper roller 8 and pretension tests lower roll 9 to roller；Receive and come from pretension
The transition roller 10 of supporter 14 to roller is tested, the slewing rollers 11 of the supporter 14 from transition roller are received, by the slewing rollers 11
Supporter 14 moved down along gravity direction and enter film-forming machine structure；Supporter 14 from film forming mechanism passes sequentially through position
Transition roller I2a, slewing rollers I1a, slewing rollers II1b and transition roller II2b in coagulation bath；By slewing rollers I1a supporter
14 move in the horizontal direction in coagulation bath, and are moved up after diverted roller II1b along gravity direction, twine supporter 14
Around on wind-up roll 5.
The pretension test tests the one end of lower roll 9 to the pretension in roller and connects encoder；Magnetic tension controller is connected to
On let off roll 4, tension sensor carrying roller 7 is provided with tension sensor.
When by pretension test to roller (including pretension tests upper roller 8 and pretension tests lower roll 9), the surface of supporter 14 is not
Uniform tension force realizes that part discharges, and thus improves the flatness of supporter 14 and ensures the uniformity of tension force.Tension sensor
Carrying roller 7 connects CZH-25 type tension sensors, and CZH-25 type tension sensors receive after tension signal, signal is fed back to
On GXFZ-B-6 type electromagnetic power brakes, the torsional forces that let off roll 6 is rotated is controlled by electromagnetic power brake, and then control
The pre-tightening tension of supporter, or set the pre-tightening tension that tension values directly control supporter by operating personnel.Pretension is tested
Lower roll 9 connects E6B2-CWZ6C type encoders, and to roller, (including pretension tests upper roller 8 and pretension is surveyed for pretension test in the course of work
Examination lower roll 9) rotation the number of turns can record by encoder and feed back in signal acquisition module realize yield record.
Said apparatus also wraps required motor and control device, the operation for controlling roller.
Supporter 14 is fixed on let off roll 6, tension sensor carrying roller 7 is passed through in the front end of supporter 14, and pretension tests the speed down
Roller 9, pretension test the speed upper roller 8, cross roller 10, slewing rollers 11, film forming mechanism 12, transition roller I2a, slewing rollers I1a, slewing rollers II1b,
Transition roller II2b, is finally fixed on wind-up roll 5.
Embodiment 1
By the performed polymer polyamic acid (PAA) of polyimides and solvent DMA (DMAc), additive third
Ketone is mixed, and the casting solution of 15%PAA+3% acetone, viscosity of sludge 8000mPas are made after heated high-speed stirred；By breadth
50cm, mesh size is that 200 μm of polythene net is that supporter is vertically arranged in the film forming of film forming mechanism and faces centre, and and motor directly
The wind-up roll connection of driving, faces film forming directly width and is set as 58cm, film forming faces spacing directly and is set as 200 microns；By casting solution
The film forming for adding film forming mechanism faces centre, static 10min directly；Motor is opened, supporter passes through film-forming machine with 15m/h linear velocity
Structure, casting solution operates in its both sides casting film-forming with supporter, stops in atmosphere after 1min, is 10%DMAc into composition
First coagulation bath of+90% pure water, winds after stopping 15 minutes, is put into the continuous progress exchange of solvent 12h of the second gel bath water relaying,
Final gel solidification forms two-sided dissymmetrical structure flat support film.
Its performance indications is as shown in table 1.
Embodiment 2~9
The step of according to embodiment 1, but casting solution in table 1 by type is provided, obtained two-sided dissymmetrical structure flat board branch
The property for supportting film is as shown in table 1
Table 1
Embodiment 10
Polyacrylonitrile (PAN) and solvent N-methyl pyrilidone (NMP), additive polyvinylpyrrolidone (PVP) are mixed
Close, 22%PAN+10%PVP casting solution, viscosity of sludge 92400mPas are made after heated high-speed stirred.By breadth
100cm, mesh size is that 50 μm of stainless steel is that supporter is vertically arranged in the film forming of film forming mechanism and faces centre directly, and is driven with motor
Dynamic wind-up roll connection, faces film forming directly width and is set as 108cm, film forming faces spacing directly and is set as 300 microns；By casting solution plus
The film forming for entering film forming mechanism faces centre, static 25min directly；Open motor, supporter with 5m/h linear velocity by film forming mechanism,
Casting solution operates in its both sides casting film-forming with supporter, stops in atmosphere after 2min, is 30%NMP+ into composition
First coagulation bath of 70% pure water, winds after stopping 15 minutes, is put into the continuous progress exchange of solvent 12h of the second gel bath water relaying,
Final gel solidification forms two-sided dissymmetrical structure flat support film.
Its performance indications is as shown in table 2.
Embodiment 11~22
The step of according to embodiment 10, but additive in table 2 by type is provided, obtained two-sided dissymmetrical structure flat board branch
The property for supportting film is as shown in table 2
Table 2
Embodiment 23
Polyether sulfone (PES) and solvent DMF (DMF), additive glycerine, NaY zeolite molecular sieve are mixed
Close, 30%PES+3% glycerine+10%NaY casting solution, viscosity of sludge 102000mPa are made after heated high-speed stirred
s.By breadth 60cm, mesh size is that 150 μm of copper mesh is that supporter is vertically arranged in the film forming of film forming mechanism and faces centre directly, and with
Motor-driven wind-up roll connection, faces film forming directly width and is set as 108cm, film forming faces spacing directly and is set as 400 microns；Will casting
The film forming that film liquid adds film forming mechanism faces centre, static 15min directly；Open motor, supporter with 10m/h linear velocity by into
Film mechanism, casting solution operates in its both sides casting film-forming with supporter, stops in atmosphere after 3min, is 50% into composition
First coagulation bath of DMF+50% water, winds after stopping 10 minutes, is put into the continuous progress exchange of solvent of the second gel bath water relaying
24h, final gel solidification forms two-sided dissymmetrical structure flat support film, and its performance indications is as shown in table 3.
Embodiment 24~29
The step of according to embodiment 23, but supporter in table 3 by type is provided, obtained two-sided dissymmetrical structure flat board branch
The property for supportting film is as shown in table 3
Table 3
Embodiment 30
Kynoar (PVDF) is mixed with solvent dimethyl sulfoxide (DMSO) (DMSO), additives polyethylene glycol, heated height
10%PVDF+10%PEG-10000 casting solution, viscosity of sludge 6000mPas are made after speed stirring.By breadth 100cm, net
Hole size is that 50 μm of titanium net is that supporter is vertically arranged in the film forming of film forming mechanism and faces centre directly, and with motor-driven wind-up roll
Connection, faces film forming directly width and is set as 108cm, film forming faces spacing directly and is set as 600 microns；Casting solution is added into film forming mechanism
Film forming face centre, static 15min directly；Open motor, supporter with 10m/h linear velocity by film forming mechanism, casting solution with
Supporter operates in its both sides casting film-forming, stops in atmosphere after 3min, in being the first coagulation bath into pure water, stops 20
Wound after minute, be put into the continuous progress exchange of solvent 24h of the second gel bath water relaying, final gel solidification forms two-sided asymmetrical junction
Structure flat support film, its performance indications is：Thickness：110 μm, molecular cut off：35KDa, pure water flux:750L/m2·h。
Embodiment 31~37
Embodiment 1~6 and 8 is prepared into two-sided dissymmetrical structure flat support polymer film to be placed in heating furnace, to
Nitrogen or air are passed through with 300mL/min flow velocity in stove, furnace temperature is warming up to 200~450 DEG C with 5 DEG C/min speed, and permanent
Temperature is after 1 hour, Temperature fall, obtains the rigid seperation film of thermic.Their performance indications such as table 4
Table 4
1GPU=1 × 10-6cm3(STP)/cm2s cm Hg≈3.36×10-10mol m-2·s-1·Pa-1
Embodiment 38~44
Embodiment 1~6 and 8 is prepared into two-sided dissymmetrical structure flat support polymer film to be placed in retort, to
Nitrogen is passed through with 300mL/min flow velocity in stove, furnace temperature is warming up to 650 DEG C with 3 DEG C/min speed, and constant temperature is after 2 hours, from
So cooling, obtains carbon membrane.Their performance indications such as table 5
Table 5
1GPU=1 × 10-6cm3(STP)/cm2s cm Hg≈3.36×10-10mol m-2·s-1·Pa-1
Embodiment 45~52
Embodiment 23~29 and 10 is prepared into two-sided dissymmetrical structure flat support polymer film model
The tensile strength of the INSTRON-5567A testing two-sided dissymmetrical structure flat support film of universal testing machine；And two-sided
Dissymmetrical structure flat support film, which is respectively put into solvent, acid or aqueous slkali, soaks 24h, the tensile strength and chemically stable measured
Property such as table 6.
Table 6
Claims (9)
1. a kind of preparation method of two-sided dissymmetrical structure flat support film, supporter is set along the direction parallel with gravity direction
Put, and two surfaces of supporter is contacted casting solution, the supporter contacted after casting solution is handled in coagulation bath,
Wherein, the casting solution, by mass percentage, is made up of following components：10%~30% polymer, 3%~20% add
Plus agent, surplus organic solvent；The viscosity of casting solution is 2000~102000mPas；
The polymer is polyimides, polyacrylonitrile, polysulfones, polyether sulfone, polyethersulfone ketone, polyethers eyeball ketone, PAEK, poly- four
PVF, Kynoar or cellulose acetate；
The additive is polyethylene glycol, polyvinylpyrrolidone, water, glycerine, butanol, ethylene glycol, acetone, lithium chloride, boiling
One or more in stone molecular sieve, nano silicon, titanium oxide, graphene, carbon nanotube；
Supporter is set to enter film formation device along the direction parallel with gravity, the film formation device includes：
Film forming mechanism, the film forming mechanism includes film forming room；Film-forming plates group in film forming room, the film-forming plates group is by two
Film forming faces relative film-forming plates composition directly, is faced directly by film forming and sets the film-forming plates parallel to gravity direction；Control device, is used for
At least two one-tenth templates are moved up in the side perpendicular to gravity direction in control film-forming plates group, and the film forming is faced directly to be hoped
The face of film forming thereon；
Impregnating mechanism, impregnating mechanism includes the container that at least one takes up coagulation bath；The impregnating mechanism, which is received, comes from film-forming machine
The supporter of structure, and make in the bath of supporter immersion precipitation；
Transport mechanism, the transport mechanism makes supporter enter film forming mechanism along the direction parallel with gravity direction, and will pass through
The supporter of film forming mechanism sends into impregnating mechanism and supporter is stopped certain time in coagulation bath.
2. according to the method described in claim 1, it is characterised in that：The organic solvent is DMA, N, N-
Dimethylformamide, 1-METHYLPYRROLIDONE or dimethyl sulfoxide (DMSO).
3. according to the method described in claim 1, it is characterised in that：The supporter is the support with uniform network structure
Body, mesh size is 10~200 μm.
4. method according to claim 1 or 2, it is characterised in that：The supporter after being contacted with casting solution is set to enter solidifying
Before glue bath, 10s~20min is stopped in air.
5. according to the method described in claim 1, it is characterised in that：The coagulation bath includes the first coagulation bath and the second gel
Bath,
First coagulation bath, by mass percentage, is made up of following components：0%~50% organic solvent and excess water, its
In, organic solvent is that DMA, DMF, chloroform, 1-METHYLPYRROLIDONE or dimethyl are sub-
Sulfone；
Second coagulation bath is water.
6. method according to claim 5, it is characterised in that：Casting solution is set to contact 10~30min with supporter；Make contact
Supported liquid membrane afterwards stops 10s~20min in atmosphere；Subsequently into the first coagulation bath, 30s~20min is stopped；Then enter
Enter in the second coagulation bath, stop 3~48h.
7. the flat support film prepared by any one of claim 1~6 methods described, it is characterised in that：The support membrane is served as reasons
The two-sided dissymmetrical structure film layer that dense layer surface, transition zone, macroporous layer, transition zone, dense layer surface are constituted successively.
8. a kind of preparation method of carbon membrane, it is characterised in that：Support membrane described in claim 7 is placed in retort, lazy
Carbonized under property atmosphere.
9. a kind of preparation method of the rigid seperation film of thermic, it is characterised in that：Support membrane described in claim 7 is placed in heating
In stove, nitrogen or air are passed through with 300mL/min flow velocity into stove, furnace temperature is warming up to 200~450 with 5 DEG C/min speed
DEG C, and constant temperature is after at least 1 hour, Temperature fall, obtains the rigid seperation film of thermic.
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| CN110845731A (en) * | 2019-11-01 | 2020-02-28 | 北京化工大学 | Method for preparing insoluble infusible polyimide film with full sponge pore structure |
| CN115245757B (en) * | 2021-04-28 | 2023-07-21 | 中国石油化工股份有限公司 | Composite nanofiltration membrane and preparation method and application thereof |
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