CN110368822A - A kind of high temperature resistant semi-aromatic seperation film and preparation method thereof - Google Patents
A kind of high temperature resistant semi-aromatic seperation film and preparation method thereof Download PDFInfo
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- CN110368822A CN110368822A CN201910732575.5A CN201910732575A CN110368822A CN 110368822 A CN110368822 A CN 110368822A CN 201910732575 A CN201910732575 A CN 201910732575A CN 110368822 A CN110368822 A CN 110368822A
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- aromatic
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- high temperature
- temperature resistant
- seperation film
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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
- 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
- B01D67/0016—Coagulation
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
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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
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention relates to technical field of polymer materials, and in particular to a kind of high temperature resistant semi-aromatic seperation film and preparation method thereof.The present invention provides a kind of preparation method of high temperature resistant semi-aromatic seperation film, the method are as follows: semiaromatic polyamide composition is first configured to casting solution, gained casting solution obtains high temperature resistant semi-aromatic seperation film using existing film-forming method again.The present invention provides a kind of preparation method of high temperature resistant semi-aromatic seperation film, and using membrane structure made from this method, complete, good hydrophilic property, heat-resisting good in thermal property, solvent resistance be good and simple process, easy to operate.
Description
Technical field
The present invention relates to technical field of polymer materials more particularly to a kind of high temperature resistant semi-aromatic seperation film and its preparations
Method.
Background technique
Semiaromatic polyamide composition improves its heat resistance due to introducing aromatic rings in aliphatic chain polyamide molecule chain structure
Its water absorption rate is reduced while with mechanical property.It therefore will by the semiaromatic polyamide composition fiber of semiaromatic polyamide composition preparation
With heat-resisting quantity and low water absorbable, while there is the advantage of workability and low cost.Semiaromatic polyamide composition fiber is opened
Hair will make up the blank field of aliphatic polyamide fiber and fully aromatic polyamide fiber, be particularly suitable for 150 DEG C or more
Hot environment or some other special environment.
Polymer separation film be the present age efficiently separate, be concentrated, purifying and cleaning equipment in a kind of material for applying, and extensively
It is general be applied to chemical industry, environmental protection, food, biology, pharmacy, electronics, electric power, metallurgy, light textile, field of seawater desalination, the contemporary energy,
It plays an important role in resource and solution problem of environmental pollution.Semiaromatic polyamide composition seperation film is a kind of novel membrane material,
Relative to common Kynoar, polysulfones, polyvinyl chloride membrane material heat resistance with higher, corrosion resistance and excellent power
Learn performance.
But semiaromatic polyamide composition film and preparation method thereof has no any report.
Summary of the invention
The present invention provides a kind of preparation method of high temperature resistant semi-aromatic seperation film, complete using membrane structure made from this method
Whole, good hydrophilic property, heat-resisting good in thermal property, solvent resistance be good and simple process, easy to operate.
Technical solution of the present invention:
The invention solves first technical problem be to provide the preparation method of high temperature resistant semi-aromatic seperation film a kind of,
The method are as follows: semiaromatic polyamide composition is first configured to casting solution, gained casting solution obtains using existing film-forming method resistance to again
High temperature semi-aromatic seperation film；Wherein, the structural formula of the semiaromatic polyamide composition is as follows:
Wherein n=10~500,0 < x+y≤1, x ≠ 0
At least one of；
R1=-(CH2)2-、-(CH2)4-、-(CH2)6-、-(CH2)9And-(CH2)10At least one of；
R2=-(CH2)4And/or-(CH2)8-；
R3=-(CH2)5-、-(CH2)6-、-(CH2)7-、-(CH2)8-、-(CH2)9-、-(CH2)10And-(CH2)11In extremely
Few one kind.
Further, the method that semiaromatic polyamide composition is configured to casting solution are as follows: by 100~400 weight of semiaromatic polyamide composition
Part and 300~1000 parts by weight of solvent are measured, are added in the dissolution kettle for having blender, thermometer, 0~60 DEG C of stirring of Yu Wendu is molten
Solution, centrifugal filtration remove solid impurity, and casting solution is made in 2~4h of standing and defoaming.
Further, the solvent be sulfuric acid, nitric acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid, hydrobromic acid extremely
Few one kind.
Further, the method for the film are as follows: use plate knifing instrument or hollow long and slender dimension film device by semi-aromatic race
Polyamide casting solution ether sulfone casting solution prepares to form flat-plate separation film and hollow-fibre membrane.
Further, the preparation method of the high temperature resistant semi-aromatic seperation film includes the following steps:
1) preparation of semiaromatic polyamide composition casting solution: by 100~400 parts by weight of semiaromatic polyamide composition and solvent 300
~1000 parts by weight are added in the dissolution kettle for having blender, thermometer, and 0~60 DEG C of stirring and dissolving of Yu Wendu, centrifugal filtration removes
Solid impurity is removed, casting solution is made in 2~4h of standing and defoaming；
2) preparation of semiaromatic polyamide composition seperation film crude product, using one of following manner:
Mode one: equably being scraped casting solution on the steel plate with flat membrane casting equipment, then primary membrane is immersed in coagulating bath admittedly
Change obtains semiaromatic polyamide composition flat-plate separation film crude product；Wherein, glass sheet temperatures: 0~60 DEG C, coagulation bath temperature -40~30
DEG C, the flow velocity of coagulating bath is 2~10m3/h；
Mode two: being sprayed above-mentioned casting solution from annular spinning head by wet spinning process, immerses coagulating bath, stretching and winding
It shapes and semiaromatic polyamide composition hollow fiber separating film crude product is made；Wherein, the ethanol solution that spinning core liquid is 50%, coagulating bath
Temperature -40~30 DEG C, the flow velocity of coagulating bath are 2~10m3/ h, spinning humidity are 50%~90%；
3) post-processing of semi-aromatic seperation film crude product:
The semiaromatic polyamide composition seperation film crude product that step 2) is prepared is subjected to washing and removes residual solvent, is then existed
Hole is protected containing protecting to impregnate in hole agent aqueous solution, High-temperature-ressemi-aromatic semi-aromatic polyamide seperation film is obtained after drying.
Further, in the step 2) of the above method, the coagulating bath is water, ethyl alcohol, acetaldehyde, cyclohexanone, N- methylpyrrole
Alkanone, dimethyl sulfoxide, diphenyl sulphone (DPS), N,N-dimethylformamide, 1,3- dimethyl-2-imidazolinone, dimethyl acetamide or
At least one of hexamethylphosphoramide；Also, it needs to add the guarantor such as sodium sulphate, zinc sulfate, lithium chloride or acetic acid hole in coagulating bath
Agent.
Further, described to protect hole agent as at least one in glycerol, ethyl alcohol, glycerine or water in the step 3) of the above method
Kind.
The invention solves second technical problem be to provide a kind of high temperature resistant semi-aromatic seperation film, use above-mentioned
Preparation method is made.
Beneficial effects of the present invention:
The present invention has been made semi-aromatic seperation film for the first time, gained film have the advantages that structural integrity, good hydrophilic property,
Heat-resisting good in thermal property, solvent resistance be good and simple process, easy to operate.
Specific embodiment
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the example ranges.
The preparation of 1 PA6T flat-plate separation film of embodiment
PA6T resin 100g and sulfuric acid 300g is added in the dissolution kettle for having blender, thermometer, is stirred at 40 DEG C of temperature
Dissolution is mixed, under vacuum conditions deaeration, cure, solution is made, which is centrifuged in centrifuge with the revolving speed of 4000r/min
Casting solution is made in 5min, filtering removal impurity, standing and defoaming 3h.
Preparation liquid is equably scraped on 0 DEG C of steel plate of temperature with flat membrane casting equipment, then primary membrane is immersed in 0 DEG C of temperature
Deionized water in, gel solidification is at PA6T flat-plate separation film；PA6T polymer separation film is washed then containing 30wt% the third three
It is impregnated in the aqueous solution of alcohol and protects hole, PA6T flat-plate separation film is obtained after drying, gained membrane structure is complete.
The structural formula of PA6T:
Obtained membrane material good hydrophilic property, water contact angle are 46 °, and film can use for a long time in 160 DEG C of temperature of environment, and
And it can the resistance to organic solvent in addition to hydrofluoric acid and the concentrated sulfuric acid etc..
The preparation of 2 PA10T hollow-fibre membrane of embodiment
PA10T resin 200g, phosphoric acid 800g are added in the dissolution kettle for having blender, thermometer, stirred at 0 DEG C of temperature
Solution is made in dissolution, under vacuum conditions deaeration, curing, which is centrifuged in centrifuge with the revolving speed of 3000r/min
Casting solution is made in 10min, filtering removal impurity, standing and defoaming 2h.
Hollow-fibre membrane is prepared by wet spinning, wherein spinning head internal diameter is 0.8mm, outer diameter 1.2mm, spinning rate
9mL/min, coagulating bath are ethyl alcohol, and spinning humidity is 60%, and core liquid is 50% second water-alcohol solution；Then by PA10T doughnut
Film impregnates in the aqueous solution of the glycerine containing 30wt% after washing protects hole, and PA10T hollow fiber separating film is obtained after drying.
The structural formula of PA10T:
Obtained membrane material good hydrophilic property, water contact angle are 63 °, and film can use for a long time in 150 DEG C of temperature of environment, and
And it can the resistance to organic solvent in addition to hydrofluoric acid and the concentrated sulfuric acid etc..
Claims (8)
1. a kind of preparation method of high temperature resistant semi-aromatic seperation film, which is characterized in that the method are as follows: first by semiaromatic adoption
Amide is configured to casting solution, and gained casting solution obtains high temperature resistant semi-aromatic seperation film using existing film-forming method again；Wherein, institute
The structural formula for stating semiaromatic polyamide composition is as follows:
Wherein n=10~500,0 < x+y≤1, x ≠ 0
At least one of；
R1=-(CH2)2-、-(CH2)4-、-(CH2)6-、-(CH2)9And-(CH2)10At least one of:
R2=-(CH2)4And/or-(CH2)8-；
R3=-(CH2)5-、-(CH2)6-、-(CH2)7-、-(CH2)8-、-(CH3)9-、(CH2)10And-(CH2)11In at least one
Kind.
2. the preparation method of high temperature resistant semi-aromatic seperation film according to claim 1, which is characterized in that semiaromatic adoption
The method that amide is configured to casting solution are as follows: by 300~1000 parts by weight of 100~400 parts by weight of semiaromatic polyamide composition and solvent,
It is added in the dissolution kettle for having blender, thermometer, 0~60 DEG C of stirring and dissolving of Yu Wendu, centrifugal filtration removes solid impurity, quiet
It sets 2~4h of deaeration and casting solution is made.
3. the preparation method of high temperature resistant semi-aromatic seperation film according to claim 2, which is characterized in that the solvent is
At least one of sulfuric acid, nitric acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid, hydrobromic acid.
4. the preparation method of described in any item high temperature resistant semi-aromatic seperation films according to claim 1~3, which is characterized in that
The method of the film are as follows: use plate knifing instrument or hollow long and slender dimension film device by semi-aromatic polyamide casting solution ether sulfone
Casting solution prepares to form flat-plate separation film and hollow-fibre membrane.
5. the preparation method of high temperature resistant semi-aromatic seperation film according to claim 4, which is characterized in that the high temperature resistant
The preparation method of semi-aromatic seperation film includes the following steps:
1) preparation of semiaromatic polyamide composition casting solution: by 100~400 parts by weight of semiaromatic polyamide composition and solvent 300~
1000 parts by weight are added in the dissolution kettle for having blender, thermometer, 0~60 DEG C of stirring and dissolving of Yu Wendu, and centrifugal filtration removes
Solid impurity, 2~4h of standing and defoaming, is made casting solution；
2) preparation of semiaromatic polyamide composition seperation film crude product, using one of following manner:
Mode one: equably being scraped casting solution on the steel plate with flat membrane casting equipment, then primary membrane is immersed in coagulating bath and is solidified
To semiaromatic polyamide composition flat-plate separation film crude product；Wherein, glass sheet temperatures: 0~60 DEG C, coagulation bath temperature -40~30 DEG C are coagulated
Admittedly the flow velocity bathed is 2~10m3/h；
Mode two: being sprayed above-mentioned casting solution from annular spinning head by wet spinning process, immerses coagulating bath, stretching and winding forming
Semiaromatic polyamide composition hollow fiber separating film crude product is made；Wherein, the ethanol solution that spinning core liquid is 50% solidifies bath temperature
- 40~30 DEG C of degree, the flow velocity of coagulating bath are 2~10m3/ h, spinning humidity are 50%~90%；
3) post-processing of semi-aromatic seperation film crude product:
The semiaromatic polyamide composition seperation film crude product that step 2) is prepared is subjected to washing and removes residual solvent, then containing guarantor
It is impregnated in hole agent aqueous solution and protects hole, High-temperature-ressemi-aromatic semi-aromatic polyamide seperation film is obtained after drying.
6. the preparation method of high temperature resistant semi-aromatic seperation film according to claim 5, which is characterized in that in step 2),
The coagulating bath is water, ethyl alcohol, acetaldehyde, cyclohexanone, N-Methyl pyrrolidone, dimethyl sulfoxide, diphenyl sulphone (DPS), N, N- dimethyl methyl
At least one of amide, 1,3- dimethyl-2-imidazolinone, dimethyl acetamide or hexamethylphosphoramide；Also, coagulating bath
In need to add sodium sulphate, zinc sulfate, lithium chloride or acetic acid.
7. the preparation method of high temperature resistant semi-aromatic seperation film according to claim 5 or 6, which is characterized in that step 3)
In, guarantor's hole agent is at least one of glycerol, ethyl alcohol, glycerine or water.
8. a kind of high temperature resistant semi-aromatic seperation film, which is characterized in that the high temperature resistant semi-aromatic seperation film is wanted using right
1~7 described in any item preparation methods are asked to be made.
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| CN201910732575.5A CN110368822A (en) | 2019-08-09 | 2019-08-09 | A kind of high temperature resistant semi-aromatic seperation film and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116531962A (en) * | 2023-07-06 | 2023-08-04 | 迈博瑞生物膜技术（南通）有限公司 | Polyamide microfiltration membrane and preparation method thereof |
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| JPS59204518A (en) * | 1983-05-09 | 1984-11-19 | Mitsui Toatsu Chem Inc | Preparation of copolymer film |
| CN102808235A (en) * | 2011-05-31 | 2012-12-05 | 上海杰事杰新材料(集团)股份有限公司 | Corrosion resisting polyamide hollow fiber film and preparation method thereof |
| CN104846473A (en) * | 2014-02-14 | 2015-08-19 | 上海特安纶纤维有限公司 | Aromatic polyamide and polyarylsulfone-based blend fiber, yarns, fabrics and products and preparation method thereof |
| CN107118344A (en) * | 2017-05-19 | 2017-09-01 | 四川大学 | A kind of anti-oxidant flame retardant type partially aromatic polyamide of color inhibition and preparation method thereof |
| CN107200856A (en) * | 2010-11-17 | 2017-09-26 | 尤尼吉可株式会社 | Semiaromatic polyamide composition film and its manufacture method |
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2019
- 2019-08-09 CN CN201910732575.5A patent/CN110368822A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204518A (en) * | 1983-05-09 | 1984-11-19 | Mitsui Toatsu Chem Inc | Preparation of copolymer film |
| CN107200856A (en) * | 2010-11-17 | 2017-09-26 | 尤尼吉可株式会社 | Semiaromatic polyamide composition film and its manufacture method |
| CN102808235A (en) * | 2011-05-31 | 2012-12-05 | 上海杰事杰新材料(集团)股份有限公司 | Corrosion resisting polyamide hollow fiber film and preparation method thereof |
| CN104846473A (en) * | 2014-02-14 | 2015-08-19 | 上海特安纶纤维有限公司 | Aromatic polyamide and polyarylsulfone-based blend fiber, yarns, fabrics and products and preparation method thereof |
| CN107118344A (en) * | 2017-05-19 | 2017-09-01 | 四川大学 | A kind of anti-oxidant flame retardant type partially aromatic polyamide of color inhibition and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116531962A (en) * | 2023-07-06 | 2023-08-04 | 迈博瑞生物膜技术（南通）有限公司 | Polyamide microfiltration membrane and preparation method thereof |
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