CN108176253A - A kind of microporous polypropylene membrane and preparation method thereof - Google Patents
A kind of microporous polypropylene membrane and preparation method thereof Download PDFInfo
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- CN108176253A CN108176253A CN201611122541.7A CN201611122541A CN108176253A CN 108176253 A CN108176253 A CN 108176253A CN 201611122541 A CN201611122541 A CN 201611122541A CN 108176253 A CN108176253 A CN 108176253A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
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- B01D2325/026—Sponge structure
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Abstract
A kind of microporous polypropylene membrane and preparation method thereof is related to a kind of polymeric membrane for separation and preparation method thereof, more particularly, to a kind of microporous polypropylene membrane prepared using environmental-friendly diluent and preparation method thereof.Diluent generally existing physiological-toxicity when the preparation method solves the problems, such as to prepare microporous polypropylene membrane using TIPS in the prior art, the extractant after extraction realize the green clean manufacturing of film-forming process by recycling.Method is easy, is suitable for commercial introduction application.There is perforation, spongy microcellular structure using microporous polypropylene membrane prepared by the method for the present invention.Microporous polypropylene membrane obtained is applicable to membrane distillation, film degassing field.
Description
Technical field
The invention belongs to polymer material science fields, are related to a kind of polymeric membrane for separation and preparation method thereof, more specifically
Ground is related to a kind of microporous polypropylene membrane and preparation method thereof.
Background technology
Polypropylene is a kind of highly crystalline thermoplastic resin being polymerized based on propylene monomer, have transparency it is high,
The excellent performances such as nontoxic, light specific gravity, easy processing, excellent in cushion effect, resistant to chemical etching, flex stiffiness, electrical insulating property be good.Due to
Its function admirable, yield are big low with price, have as the membrane material for preparing microporous barrier and have great advantage.
In the technical field of microporous polypropylene membrane is prepared using TIPS methods (thermally induced phase separation), it should fully adjustment system
Film parameters are to control membrane structure and pattern so as to adjust film properties, concentration, polymer such as polymer type and in casting solution
Molecular weight, diluent type and concentration, diluent molecule amount, the melting temperature of system and time, additive, cooling condition, extraction
Taking and dry etc. can prepare microporous polypropylene membrane to thermally induced phase separation and have an impact.Wherein diluent is film-made in TIPS methods
During play an important role.
The diluent that the prior art uses is diluent system (such as two fourth of phthalic acid containing phthalic acid ester mostly
Ester) and containing the irritating diluent system of diphenyl ether.This kind of diluent generally existing physiological-toxicity has intense stimulus
Smell.Studying tissue identification by international cancer has experimental animal or the mankind influences such as carcinogenic or damage fecundity.To mesh
Before until, there are reproductions and environmental toxicity mostly for the solvent used in film-forming process, and health of human body and Environmental security are caused
Detrimental effect.
When Chinese patent 103785303 prepares polypropylene hollow fiber hydrophobic membrane using thermally induced phase separation, employ and contain
There is the carcinogenic teratogenesis substance of phthalic acid ester as coagulating bath medium.Patent CN101862601A discloses a kind of polypropylene
Hollow fiber microporous membrane and preparation method thereof, using dibutyl phthalate, fatty amine, calcium stearate, isopropyl amine alcohol, methyl
The combination of one or more of phenylpropyl alcohol ester, vegetable oil or diphenyl ether is as diluent.Patent CN201210434202.8 is disclosed
A kind of preparation method and application of polypropylene hollow fiber hydrophobic membrane is made using the mixture of vegetable oil and phthalate
For diluent.Patent CN1356410A discloses a kind of method that thermally induced phase separation prepares microporous polypropylene membrane, using plant
As diluent, adipic acid, benzoic acid are made homogeneous phase solution, pass through spinneret as auxiliary agent for oil, atoleine, diphenyl ether, machine oil
Head is spun into polypropylene hollow fiber silk, is solidified into water, and using extraction, polypropylene hollow fiber membrane is made.Patent
00802940.7 and patent 00802939.3 also disclose a kind of be used for through the entirety of thermal induction Liquid liquid Separation gas exchanges
The preparation method of asymmetric polyolefin hydrophobic membrane, using the mixed solvent system of two kinds of compound compositions of A and B, compound A is poly-
The Weak solvent of object is closed, compound B is the non-solvent of polymer.Wherein for polypropylene, 00802940.7 useization of patent and object A
For soybean oil, palm-kernel oil, dioctyl phthalate, N, bis- (2- ethoxys) tallow amines of N- or its mixture.Compound B is
Dibutyl phthalate, diethyl phthalate, glycerol triacetate, castor oil or its mixture.Patent
00802939.3 by N, bis- (2- ethoxys) tallow amines of N-, dioctyl phthalate, soybean oil, palm-kernel oil or its mixture
As compound A, dibutyl phthalate, diethyl phthalate, triethylglycerides, castor oil or its mixture are used
Make polyacrylic compound B.
These diluents have drawn attention in film to the harmful effect of environment, strictly speaking, such membrane process
The clean process of green cannot be referred to as.Especially when enviromental protection law is increasingly strict, environment amenable green solvent
Or the demand of low toxicity, low harmful solvent will be increasingly stronger.Therefore the present invention staff is intended to research and uses environmental-friendly diluent
Microporous polypropylene membrane is prepared by TIPS methods.
Invention content
To overcome technical problem in the prior art, the present invention provides a kind of polypropylene prepared using TIPS methods
Microporous barrier, by controlling the composition of casting solution, the type of concentration, diluent, the composition of diluent and content including polymer,
And Thermal inactive membrance casting condition includes that extrusion temperature, cooling condition, that extraction conditions obtains the preferable polypropylene of hydrophobicity is micro-
Pore membrane.
The present invention also provides it is a kind of by thermally induced phase separation prepare environmental-friendly microporous polypropylene membrane method,
This method is made casting solution after mixing acrylic resin, environmental-friendly diluent and filters, by casting solution through slit mould
Head squeezes out, then microporous polypropylene membrane precursor is made through cooling and solidifying, and after which is wound with up- coiler, is put into
It is extracted in microporous membrane extraction device with extractant, the freeze-dried device drying of the film after extraction obtains microporous polypropylene membrane.With
Film section prepared by this method has perforation, spongiform asymmetric homogeneous microcellular structure, solves and uses in the prior art
When TIPS prepares polypropylene hollow fiber membrane, diluent generally existing physiological-toxicity or with intense stimulus smell the problem of.
After extraction equipment is handled, the extractant of recycling can be recycled for extractant and diluent.It is micro- to additionally provide the polypropylene
The purposes that pore membrane deaerates for membrane distillation, film.
To achieve the above objectives, the technical solution used in the present invention is：
A kind of microporous polypropylene membrane, including：Acrylic resin,
The contact angle of the microporous polypropylene membrane is 120 ° -140 °, and average pore size is 0.01-0.04 μm.
The preparation method of above-mentioned microporous polypropylene membrane, includes the following steps：
Casting solution is made after mixing acrylic resin and diluent in step a；
Step b, casting solution is filtered；
Casting solution after filtering is delivered to slit coventry type die head coventry, is squeezed out before obtaining plate membrane through slit coventry type die head coventry by step c
Then plate membrane precursor is immersed in coagulating bath and is cooled to curing, obtains microporous polypropylene membrane precursor by body；
Step d after microporous polypropylene membrane precursor is wound with up- coiler, is put into microporous membrane extraction device and is extracted with extractant
It takes；
Step e, the freeze-dried device drying of microporous barrier precursor after extraction, after removing extractant, it is micro- to be made polypropylene
Pore membrane.
On the basis of said program, in step a, after acrylic resin and diluent are mixed, under vacuum,
Casting solution is made in standing and defoaming after heating stirring.
On the basis of said program, the condition that casting solution is made is：Heating temperature be 175~200 DEG C, pressure for-
0.095MPa, mixing time are 0.5~12h, and inclined heated plate is 0.5~12h.
On the basis of said program, in casting solution described in step a, the content of acrylic resin is 20~35wt%, excellent
22.5~27.5wt% is selected, amount of diluent is 65~80wt%, preferably 72.5~77.5wt%.
On the basis of said program, mixture of the diluent described in step a for A and B compositions, A is in diluent
Content is liquid under the heating temperature and dissolves each other that wherein A is the bad of acrylic resin for 10wt%~45wt%, A and B
Solvent, B are the good solvent of acrylic resin, and B has adjusted acrylic resin and the interaction parameter of A.
On the basis of said program, the A is extracted from natural plants or animal product and is obtained, and is babassu
One kind in wax, small candle number wax or beeswax；The B is one kind in soybean oil or peanut oil.
On the basis of said program, the slit gap distance of slit coventry type die head coventry described in step c be 2~10mm, die head temperature
It is 140~175 DEG C to spend, and preferable temperature is 145~165 DEG C.
On the basis of said program, plate membrane precursor described in step c is first through the air-cooled cooling of air, then in chill roll
Upper winding, then immerse in coagulating bath and be cooled to curing, obtain microporous polypropylene membrane precursor.
On the basis of said program, the coagulating bath is twin-stage coagulating bath；Casting solution passes through after slit coventry type die head coventry extrusion
Cross twin-stage coagulating bath.
On the basis of said program, the first order coagulating bath in the twin-stage coagulating bath is air-cooled for air, the twin-stage
The temperature of second level coagulating bath in coagulating bath is 0~25 DEG C, the type of second level coagulating bath component be it is close with diluent or
Compatible system, the type of second level coagulating bath component is air or vegetable oil.
On the basis of said program, the vegetable oil is one in soybean oil, castor oil, corn oil or palm-kernel oil
Kind, preferably soybean oil.
On the basis of said program, extractant described in step d be boiling alcohols material or warm chloroform, it is described
Alcohols material is preferably ethyl alcohol or isopropanol, and the chloroform of the warm, heating temperature is 30~50 DEG C.
On the basis of said program, extraction time described in step d be 3~8h, the recyclable recycling of extractant.
In one embodiment of the invention, in microporous membrane extraction device, using the ethyl alcohol of boiling, 3~8h, extraction are extracted
The film taken takes out freeze-dried machine drying, and after removing extractant, microporous polypropylene membrane is made.Ethanol recovery after extraction
99%.
In the film-forming process for causing phase separation in thermal induction, the type temperature that process control condition also has coagulating bath (influences film
Outer surface) and its cooldown rate selection, the phase separation of these factors influence casting solutions, so influence film structure shape
State.
When preparing polypropylene hollow fiber membrane using TIPS in the prior art, diluent generally existing physiological-toxicity or tool
There is intense stimulus smell.The present invention uses the method for environmental-friendly diluent film to prepare polypropylene using thermally induced phase separation
Microporous barrier provides a kind of completely new method and approach.
Advantageous effect：
The present invention has following improvement compared with prior art, and the present invention is used by selecting a kind of environmental-friendly diluent
Thermal phase separation process prepares microporous polypropylene membrane, and the concentration of polymer is included by the composition for controlling casting solution, diluent
Composition and content and Thermal inactive membrance casting condition include extrusion temperature, cooling medium, cooling temperature, extraction and processing item
Part obtains the preferably environmentally friendly microporous polypropylene membrane of hydrophobicity.The preparation method solves to prepare using TIPS in the prior art
During polypropylene hollow fiber membrane the problem of diluent generally existing physiological-toxicity, the extractant after extraction passes through recycling,
Realize the green clean manufacturing of film-forming process.Have using microporous polypropylene membrane prepared by the method for the present invention and penetrate through, is spongy
The surface that microcellular structure section and micropore are evenly distributed.Microporous polypropylene membrane obtained is applicable to membrane distillation, film degassing field.
Method is easy, is suitable for commercial introduction application.
Description of the drawings
The present invention has drawings described below：
Fig. 1-Fig. 3 is the stereoscan photograph of film section made from embodiment 4.
The amplification factor that the amplification factor that wherein amplification factor of Fig. 1 is 500, Fig. 2 is 2000, Fig. 3 is 5000；
Fig. 4-Fig. 6 is the stereoscan photograph of film section made from comparative example 1.
The amplification factor that the amplification factor that wherein amplification factor of Fig. 4 is 400, Fig. 5 is 2000, Fig. 6 is 5000.
Specific embodiment
To make the present invention easier to understand, below in conjunction with drawings and examples, the present invention will be described in detail, these realities
Apply example only serve it is illustrative, it is not limited to application range of the invention, unmentioned specific experiment side in the following example
Method is usually carried out according to routine experiment method.
A kind of microporous polypropylene membrane, including：Acrylic resin,
The contact angle of the microporous polypropylene membrane is 120 ° -140 °, and average pore size is 0.01-0.04 μm.
The preparation method of above-mentioned microporous polypropylene membrane, includes the following steps：
Casting solution is made after mixing acrylic resin and diluent in step a；
Step b, casting solution is filtered；
Casting solution after filtering is delivered to slit coventry type die head coventry, is squeezed out before obtaining plate membrane through slit coventry type die head coventry by step c
Then plate membrane precursor is immersed in coagulating bath and is cooled to curing, obtains microporous polypropylene membrane precursor by body；
Step d after microporous polypropylene membrane precursor is wound with up- coiler, is put into microporous membrane extraction device and is extracted with extractant
It takes；
Step e, the freeze-dried device drying of microporous barrier precursor after extraction, after removing extractant, it is micro- to be made polypropylene
Pore membrane.
On the basis of said program, in step a, after acrylic resin and diluent are mixed, under vacuum,
Casting solution is made in standing and defoaming after heating stirring.
On the basis of said program, the condition that casting solution is made is：Heating temperature be 175~200 DEG C, pressure for-
0.095MPa, mixing time are 0.5~12h, and inclined heated plate is 0.5~12h.
On the basis of said program, in casting solution described in step a, the content of acrylic resin is 20~35wt%, excellent
22.5~27.5wt% is selected, amount of diluent is 65~80wt%, preferably 72.5~77.5wt%.
On the basis of said program, mixture of the diluent described in step a for A and B compositions, A is in diluent
Content is liquid under the heating temperature and dissolves each other that wherein A is the bad of acrylic resin for 10wt%~45wt%, A and B
Solvent, B are the good solvent of acrylic resin, and B has adjusted acrylic resin and the interaction parameter of A.
On the basis of said program, the A is extracted from natural plants or animal product and is obtained, and is babassu
One kind in wax, small candle number wax or beeswax；The B is one kind in soybean oil or peanut oil.
On the basis of said program, the slit gap distance of slit coventry type die head coventry described in step c be 2~10mm, die head temperature
It is 140~175 DEG C to spend, and preferable temperature is 145~165 DEG C.
On the basis of said program, plate membrane precursor described in step c is first through the air-cooled cooling of air, then in chill roll
Upper winding, then immerse in coagulating bath and be cooled to curing, obtain microporous polypropylene membrane precursor.
On the basis of said program, the coagulating bath is twin-stage coagulating bath；Casting solution passes through after slit coventry type die head coventry extrusion
Cross twin-stage coagulating bath.
On the basis of said program, the first order coagulating bath in the twin-stage coagulating bath is air-cooled for air, the twin-stage
The temperature of second level coagulating bath in coagulating bath is 0~25 DEG C, the type of second level coagulating bath component be it is close with diluent or
Compatible system, the type of second level coagulating bath component is air or vegetable oil.
On the basis of said program, the vegetable oil is one in soybean oil, castor oil, corn oil or palm-kernel oil
Kind, preferably soybean oil.
On the basis of said program, extractant described in step d be boiling alcohols material or warm chloroform, it is described
Alcohols material is preferably ethyl alcohol or isopropanol, and the chloroform of the warm, heating temperature is 30~50 DEG C.
On the basis of said program, extraction time described in step d be 3~8h, the recyclable recycling of extractant.
Embodiment 1
A kind of microporous polypropylene membrane, 0.04 μm of average pore size, 125.6 ° of contact angle, preparation method is as follows：Heating temperature
It it is 175~200 DEG C, pressure is -0.095MPa, and mixing time is 0.5~12h, and inclined heated plate is 0.5~12h.
The slit gap distance of slit coventry type die head coventry described in step c is 2~10mm, and die head temperature is 140~175 DEG C, preferably
Temperature is 145~165 DEG C.
The alcohols material is preferably ethyl alcohol or isopropanol, and the chloroform of the warm, heating temperature is 30~50 DEG C.
(1) in the kettle with agitating device add in 20wt% acrylic resin and 80wt% Brazil wax and
The mixed diluent of soybean oil, content of the Brazil wax in diluent are 10wt%.Be heated to 175 DEG C, pressure-
Under the conditions of 0.095MPa, 1.5h is stirred, after stopping stirring, under -0.095MPa pressure, constant temperature standing and defoaming 1.5h is cast
Film liquid；
(2) casting solution that temperature is 175 DEG C through 100 mesh stainless steel filter screens is filtered, is squeezed out through slit coventry type die head coventry, slit
Clearance distance 2mm, die head temperature are 160 DEG C, and the plate membrane precursor of extrusion is first through the air-cooled cooling of air, then on chill roll
Winding is immersed in twin-stage coagulating bath and is cooled down, and the first order coagulating bath in twin-stage coagulating bath is air-cooled for air, second level coagulating bath group
It is divided into air, temperature is 0 DEG C, and Polypropylene plates microporous barrier precursor is obtained after cooling.
(3) Polypropylene plates microporous barrier precursor is wound by up- coiler, is placed into microporous membrane extraction device with boiling
Ethyl alcohol is extracted as extractant, is extracted 3 hours；
(4) film of the moistening obtained after extracting takes out freeze-dried machine drying, and after removing extractant, it is micro- that polypropylene is made
Pore membrane.Ethanol recovery 90%.
(5) Polypropylene plates microporous barrier is obtained after drying.
Contact angle test method：Using contact angle tester, 1~180 ° of measurement range, resolution ratio ± 0.1 °, using static state
Sitting-drop methods, each fixed volume be 2 μ L deionized water drop, drip in film wire, take calculating initial contact angle be doughnut
The Contact-angle measurement value of film wire, horizontal survey 6 times calculate average value.
Membrane distillation permeant flux (J) test method：10 hollow fiber film threads are taken, are fabricated to membrane module, using 1wt% chlorine
Change sodium-salt aqueous solution and carry out vacuum membrane distillation test, in 80 DEG C of feeding temperature, vacuumizing pressure -0.09MPa, cross-flow filtration,
Flow velocity 0.62cm/s.The production water obtained in certain time is collected, membrane distillation permeant flux is calculated by the following formula (1), measures 3
It is secondary, calculate average value.
Wherein W, A, and t represent production water weight, effective membrane area and interval production water time respectively.Salt rejection rate (R) test side
Method：Using the conductivity of conductivity meter test material liquid and production water, pass through formula (2) and calculate
Wherein, Cp、CbRepresent the conductivity of production water and material liquid.
Minimum-value aperture and air penetrability (P, unit cm3/(cm2﹒ s ﹒ bar), test method：Using bubble platen press membrane aperture analyzer
Test.
After tested, vacuum membrane distillation permeant flux is 5.55L/ (m2H), salt rejection rate 99.83%.Air penetrability 0.88cm3/
(cm2﹒ s ﹒ bar).
Embodiment 2
A kind of microporous polypropylene membrane, 0.033 μm of average pore size, 140.0 ° of contact angle, preparation method is as follows：
(1) in the kettle with agitating device add in 30wt% acrylic resin and 70wt% Brazil wax and
The mixed diluent of soybean oil, content of the Brazil wax in diluent are 20wt%.Be heated to 180 DEG C, pressure-
Under the conditions of 0.095MPa, 0.5h is stirred, after stopping stirring, under -0.095MPa pressure, constant temperature standing and defoaming 0.5h is cast
Film liquid；
(2) casting solution that temperature is 180 DEG C through 100 mesh stainless steel filter screens is filtered, is squeezed out through slit coventry type die head coventry, slit
Clearance distance 4mm, die head temperature are 140 DEG C, and the plate membrane precursor of extrusion is first through the air-cooled cooling of air, then on chill roll
Winding is immersed in twin-stage coagulating bath and is cooled down, and the first order coagulating bath in twin-stage coagulating bath is air-cooled for air, second level coagulating bath group
It is soybean oil to divide, and temperature is 25 DEG C, and Polypropylene plates microporous barrier precursor is obtained after cooling.
(3) Polypropylene plates microporous barrier precursor is wound by up- coiler, is placed into microporous membrane extraction device with boiling
Isopropanol is extracted as extractant, is extracted 4 hours；
(4) the freeze-dried machine drying of the taking-up of moistening obtained after extracting, after removing extractant, is made polypropylene microporous
Film.Isopropanol recovering rate 90%.
(5) Polypropylene plates microporous barrier is obtained after drying.
After tested, vacuum membrane distillation permeant flux is 9.84L/ (m2H), salt rejection rate 99.78%.Air penetrability 0.88cm3/
(cm2﹒ s ﹒ bar).
Embodiment 3
A kind of microporous polypropylene membrane, 0.033 μm of average pore size, 129.9 ° of contact angle, preparation method is as follows：
(1) acrylic resin of 22.5wt% and the babassu of 77.5wt% are added in the kettle with agitating device
The mixed diluent of wax and soybean oil, content of the Brazil wax in diluent are 30wt%.Be heated to 190 DEG C, pressure-
Under the conditions of 0.095MPa, 2h is stirred, after stopping stirring, under -0.095MPa pressure, constant temperature standing and defoaming 2h obtains casting solution；
(2) casting solution that temperature is 190 DEG C through 100 mesh stainless steel filter screens is filtered, is squeezed out through slit coventry type die head coventry, slit
Clearance distance 6mm, die head temperature are 150 DEG C, and the plate membrane precursor of extrusion is first through the air-cooled cooling of air, then on chill roll
Winding is immersed in twin-stage coagulating bath and is cooled down, and the first order coagulating bath in twin-stage coagulating bath is air-cooled for air, second level coagulating bath group
It is castor oil to divide, and temperature is 15 DEG C, and Polypropylene plates microporous barrier precursor is obtained after cooling.
(3) Polypropylene plates microporous barrier precursor is wound by up- coiler, is placed into microporous membrane extraction device and is with temperature
50 DEG C of chloroform is extracted as extractant, is extracted 5 hours；
(4) film of the moistening obtained after extracting takes out freeze-dried machine drying, and after removing extractant, it is micro- that polypropylene is made
Pore membrane.The chloroform rate of recovery 90%.
(5) Polypropylene plates microporous barrier is obtained after drying.
After tested, vacuum membrane distillation permeant flux is 5.85L/ (m2H), salt rejection rate 98.15%.Air penetrability 0.88cm3/
(cm2﹒ s ﹒ bar).
Embodiment 4
A kind of microporous polypropylene membrane, 0.03 μm of average pore size, 125.7 ° of contact angle, preparation method is as follows：
(1) in the kettle with agitating device add in 30wt% acrylic resin and 70wt% Brazil wax and
The mixed diluent of soybean oil, content of the Brazil wax in diluent are 35wt%.Be heated to 185 DEG C, pressure-
Under the conditions of 0.095MPa, 1.5h is stirred, after stopping stirring, under -0.095MPa pressure, constant temperature standing and defoaming 1.5h is cast
Film liquid；
(2) casting solution that temperature is 185 DEG C through 100 mesh stainless steel filter screens is filtered, is squeezed out through slit coventry type die head coventry, slit
Clearance distance 8mm, die head temperature are 145 DEG C, and the plate membrane precursor of extrusion is first through the air-cooled cooling of air, then on chill roll
Winding is immersed in twin-stage coagulating bath and is cooled down, and the first order coagulating bath in twin-stage coagulating bath is air-cooled for air, second level coagulating bath group
It is corn oil to divide, and temperature is 15 DEG C, and Polypropylene plates microporous barrier precursor is obtained after cooling.
(3) Polypropylene plates microporous barrier precursor is wound by up- coiler, is placed into microporous membrane extraction device and is with temperature
40 DEG C of chloroform is extracted as extractant, is extracted 6 hours；
(4) film of the moistening obtained after extracting takes out freeze-dried machine drying, and after removing extractant, it is micro- that polypropylene is made
Pore membrane.The chloroform rate of recovery 90%.
(5) Polypropylene plates microporous barrier is obtained after drying, film section SEM photograph is shown in Fig. 1-3.
After tested, vacuum membrane distillation permeant flux is 7.47L/ (m2H), salt rejection rate 99.91%.Air penetrability 1.13cm3/
(cm2﹒ s ﹒ bar).
Embodiment 5
A kind of microporous polypropylene membrane, 0.01 μm of average pore size, 128.4 ° of contact angle, preparation method is as follows：
(1) in the kettle with agitating device add in 35wt% acrylic resin and 65wt% Brazil wax and
The mixed diluent of soybean oil, content of the Brazil wax in diluent are 40wt%.Be heated to 200 DEG C, pressure-
Under the conditions of 0.095MPa, 6h is stirred, after stopping stirring, under -0.095MPa pressure, constant temperature standing and defoaming 4h obtains casting solution；
(2) casting solution that temperature is 200 DEG C through 100 mesh stainless steel filter screens is filtered, is squeezed out through slit coventry type die head coventry, slit
Clearance distance 10mm, die head temperature are 165 DEG C, and the plate membrane precursor of extrusion is first through the air-cooled cooling of air, then in chill roll
Upper winding is immersed in twin-stage coagulating bath and is cooled down, and the first order coagulating bath in twin-stage coagulating bath is air-cooled for air, second level coagulating bath
Component is palm-kernel oil, and temperature is 25 DEG C, and Polypropylene plates microporous barrier precursor is obtained after cooling.
(3) Polypropylene plates microporous barrier precursor is wound by up- coiler, is placed into microporous membrane extraction device and is with temperature
30 DEG C of chloroform is extracted as extractant, is extracted 7 hours；
(4) film of the moistening obtained after extracting takes out freeze-dried machine drying, and after removing extractant, it is micro- that polypropylene is made
Pore membrane.The chloroform rate of recovery 90%.
(5) Polypropylene plates microporous barrier is obtained after drying.
After tested, vacuum membrane distillation permeant flux is 9.22L/ (m2H), salt rejection rate 99.94%.Air penetrability 2.00cm3/
(cm2﹒ s ﹒ bar).
Embodiment 6
A kind of microporous polypropylene membrane, 0.04 μm of average pore size, 120 ° of contact angle, preparation method is as follows：
(1) acrylic resin of 27.5wt% and the babassu of 72.5wt% are added in the kettle with agitating device
The mixed diluent of wax and soybean oil, content of the Brazil wax in diluent are 45wt%.Be heated to 195 DEG C, pressure-
Under the conditions of 0.095MPa, 8h is stirred, after stopping stirring, under -0.095MPa pressure, constant temperature standing and defoaming 5h obtains casting solution；
(2) casting solution that temperature is 195 DEG C through 100 mesh stainless steel filter screens is filtered, is squeezed out through slit coventry type die head coventry, slit
Clearance distance 2mm, die head temperature are 170 DEG C, and the plate membrane precursor of extrusion is first through the air-cooled cooling of air, then on chill roll
Winding is immersed in twin-stage coagulating bath and is cooled down, and the first order coagulating bath in twin-stage coagulating bath is air-cooled for air, second level coagulating bath group
It is soybean oil to divide, and temperature is 15 DEG C, and Polypropylene plates microporous barrier precursor is obtained after cooling.
(3) Polypropylene plates microporous barrier precursor is wound by up- coiler, is placed into microporous membrane extraction device with boiling
Ethyl alcohol is extracted as extractant, is extracted 8 hours；
(4) film of the moistening obtained after extracting takes out freeze-dried machine drying, and after removing extractant, it is micro- that polypropylene is made
Pore membrane.Ethanol recovery 90%.
(5) Polypropylene plates microporous barrier is obtained after drying.
After tested, vacuum membrane distillation permeant flux is 7.31L/ (m2H), salt rejection rate 99.98%.Air penetrability 0.94cm3/
(cm2﹒ s ﹒ bar).
Embodiment 7
A kind of microporous polypropylene membrane, 0.03 μm of average pore size, 128 ° of contact angle, preparation method is as follows：
(1) acrylic resin of 30wt% and the beeswax and peanut oil of 70wt% are added in the kettle with agitating device
Mixed diluent, content of the beeswax in diluent be 30wt%.185 DEG C are heated to, under the conditions of pressure -0.095MPa,
5h is stirred, after stopping stirring, under -0.095MPa pressure, constant temperature standing and defoaming 6h obtains casting solution；
(2) casting solution that temperature is 185 DEG C through 100 mesh stainless steel filter screens is filtered, is squeezed out through slit coventry type die head coventry, slit
Clearance distance 2mm, die head temperature are 175 DEG C, and the plate membrane precursor of extrusion is first through the air-cooled cooling of air, then on chill roll
Winding is immersed in twin-stage coagulating bath and is cooled down, and the first order coagulating bath in twin-stage coagulating bath is air-cooled for air, second level coagulating bath group
It is soybean oil to divide, and temperature is 0 DEG C, and Polypropylene plates microporous barrier precursor is obtained after cooling.
(3) Polypropylene plates microporous barrier precursor is wound by up- coiler, is placed into microporous membrane extraction device with boiling
Ethyl alcohol is extracted as extractant, is extracted 3 hours；
(4) film of the moistening obtained after extracting takes out freeze-dried machine drying, and after removing extractant, it is micro- that polypropylene is made
Pore membrane.Ethanol recovery 90%.
(5) Polypropylene plates microporous barrier is obtained after drying.
After tested, vacuum membrane distillation permeant flux is 7.88L/ (m2H), salt rejection rate 99.98%.Air penetrability 1.86cm3/
(cm2﹒ s ﹒ bar).
Embodiment 8
A kind of microporous polypropylene membrane, 0.038 μm of average pore size, 133 ° of contact angle, preparation method is as follows：
The acrylic resin of 35wt% and small candle number wax and the soybean of 65wt% are added in the kettle with agitating device
The mixed diluent of oil, content of the small candle number wax in diluent is 45wt%.185 DEG C are heated to, in pressure -0.095MPa items
Under part, 12h is stirred, after stopping stirring, under -0.095MPa pressure, constant temperature standing and defoaming 12h obtains casting solution；
Other steps obtain Polypropylene plates microporous barrier with embodiment 7.
After tested, vacuum membrane distillation permeant flux is 8.25L/ (m2H), salt rejection rate 99.58%.Air penetrability 1.36cm3/
(cm2﹒ s ﹒ bar).
Comparative example 1
A kind of microporous polypropylene membrane, 0.063 μm of average pore size, 114 ° of contact angle, preparation method is as follows：
The acrylic resin of 30wt% and the soybean oil diluent of 70wt% are added in the kettle with agitating device.Add
Heat is to 185 DEG C, under the conditions of pressure -0.095MPa, stirs 1.5h, after stopping stirring, under -0.095MPa pressure, constant temperature is quiet
Deaeration 1.5h is put, obtains casting solution；Other steps obtain Polypropylene plates microporous barrier with embodiment 4.Film shape obtained is concave-convex
Injustice, it is hard and crisp.Film section SEM photograph is shown in Fig. 4-6.
The content not being described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.
Claims (10)
1. a kind of microporous polypropylene membrane, it is characterised in that：Including：Acrylic resin, the contact angle of the microporous polypropylene membrane are
120 ° -140 °, average pore size is 0.01-0.04 μm.
2. the preparation method of microporous polypropylene membrane as described in claim 1, it is characterised in that：Include the following steps：
Casting solution is made after mixing acrylic resin and diluent in step a；
Step b, casting solution is filtered；
Casting solution after filtering is delivered to slit coventry type die head coventry by step c, squeezes out to obtain plate membrane precursor through slit coventry type die head coventry, so
Plate membrane precursor is immersed in coagulating bath afterwards and is cooled to curing, obtains microporous polypropylene membrane precursor；
Step d after microporous polypropylene membrane precursor is wound with up- coiler, is put into microporous membrane extraction device and is extracted with extractant；
Step e, the freeze-dried device drying of microporous barrier precursor after extraction, after removing extractant, is made microporous polypropylene membrane.
3. the preparation method of microporous polypropylene membrane as claimed in claim 2, it is characterised in that：In step a, by acrylic resin
And after diluent mixing, under vacuum, casting solution is made in standing and defoaming after heating stirring.
4. the preparation method of microporous polypropylene membrane as claimed in claim 3, it is characterised in that：Be made casting solution condition be：
Heating temperature is 175~200 DEG C, and pressure is -0.095MPa, and mixing time is 0.5~12h, and inclined heated plate is 0.5~12h.
5. the preparation method of microporous polypropylene membrane as claimed in claim 2, it is characterised in that：In casting solution described in step a, gather
The content of allyl resin is 20~35wt%, and amount of diluent is 65~80wt%.
6. the preparation method of microporous polypropylene membrane as claimed in claim 4, it is characterised in that：Diluent described in step a is A
With the mixture of B compositions, the A is extracted from natural plants or animal product and is obtained, and is Brazil wax, small candle number wax
Or one kind in beeswax, contents of the A in diluent are 10wt%~45wt%, the B is one in soybean oil or peanut oil
Kind；A and B is liquid under the heating temperature and dissolves each other that wherein A is the poor solvent of acrylic resin.
7. the preparation method of microporous polypropylene membrane as claimed in claim 2, it is characterised in that：Slit coventry type die head coventry described in step c
Slit gap distance for 2~10mm, die head temperature is 140~175 DEG C.
8. the preparation method of microporous polypropylene membrane as claimed in claim 2, it is characterised in that：Plate membrane precursor described in step c
First through the air-cooled cooling of air, then wound on chill roll, then immerse in coagulating bath and be cooled to curing, obtain polypropylene microporous
Film precursor.
9. the preparation method of microporous polypropylene membrane as claimed in claim 2, it is characterised in that：The coagulating bath is solidified for twin-stage
Bath；First order coagulating bath in the twin-stage coagulating bath is air-cooled for air, the second level coagulating bath in the twin-stage coagulating bath
Temperature is 0~25 DEG C, and the type of second level coagulating bath component is the system close or compatible with diluent, second level coagulating bath group
Point type be air either the vegetable oil vegetable oil be in soybean oil, castor oil, corn oil or palm-kernel oil one
Kind.
10. the preparation method of microporous polypropylene membrane as claimed in claim 2, it is characterised in that：Extractant described in step d is boiling
The alcohols material or the chloroform of warm risen, the chloroform of the warm, heating temperature are 30~50 DEG C, and the extraction time is 3
~8h, the recyclable recycling of extractant.
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| CN104248916A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Polypropylene separation membrane and preparation method thereof |
| CN105381723A (en) * | 2014-09-05 | 2016-03-09 | 中国石油化工股份有限公司 | Super-hydrophobic flat plate membrane preparation method |
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| US6180008B1 (en) * | 1998-07-30 | 2001-01-30 | W. R. Grace & Co.-Conn. | Polyimide membranes for hyperfiltration recovery of aromatic solvents |
| CN1356410A (en) * | 2001-12-19 | 2002-07-03 | 天津大学 | Thermal phase-separating process for preparing microporous film of hollow polypropylene fibres |
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