CN1400038A - Production method of macromolecular nano filtering membrane - Google Patents
Production method of macromolecular nano filtering membrane Download PDFInfo
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- CN1400038A CN1400038A CN 01126384 CN01126384A CN1400038A CN 1400038 A CN1400038 A CN 1400038A CN 01126384 CN01126384 CN 01126384 CN 01126384 A CN01126384 A CN 01126384A CN 1400038 A CN1400038 A CN 1400038A
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Abstract
The production method of macromolecular nano filtration membrane includes the following steps: mixing nano-grade inorganic material powder, inorganic material powder body with nano-grade microporous skeletal structure, polyolefine and working adjuvant to obtain mixed material; extruding the mixed material by means of twin screw extruder; feeding the extruded material into calender for calendering and forming membrane; finally cleaning the formed membrane and drying so as to obtain said invented product. Its production process is simple and cost is low.
Description
Technical field
The present invention relates to a kind of manufacture method of macromolecular nano filtering membrane.
Background technology
Macromolecular nano filtering membrane is a most important film in the membrane separation technique, has been widely used in chemical industry, electronics, light industry, weaving, metallurgy, food, field of petrochemical industry at present.Existing macromolecular nano filtering film manufacturing method mainly comprises following several:
1) macromolecule is dissolved in makes solution in the solvent,, allow the solvent evaporation then, form uniform macromolecular nano filtering membrane onboard again with Polymer Solution casting film-forming on glass plate or steel plate.The film that this method is made, its macromolecule resin should have fine solubility.
2) charged particle with nuclear reactor shines polymeric membrane, stays the sensitization track, makes the fracture of film inner macromolecule chain link, uses the nuclear track of sensitization in the solution etching macromolecule again, forms the hole, makes macromolecular nano filtering membrane.The length control of the length of the number of this fenestra and the size in hole difference exposure time and etch period.This film principal item has Merlon and poly-ethyl ester film.
3) with the crystalline state macromolecule of high-strength directional, under near its melting temperature, the extruding film forming is pulled out simultaneously fast, carries out secondary after the cooling and extends, and makes the membrane crystallization structure impaired, produces the crack, and pore-forming is made macromolecular nano filtering membrane.This film mainly is polyethylene, polypropylene, poly tetrafluoroethylene.
4) the homogeneous membrane liquid curtain coating that will heat preparation become thin after, the precipitation phase-splitting takes place in cooling, liquid film, and film forming, pore-forming, makes macromolecular nano filtering membrane.The size of this film fenestra is influenced by settling velocity mainly, and the slow more fenestra of settling velocity is big more.Polypropylene and polyvinylidene fluoride microporous film are its most important products.
5) macromolecule is annotated in mixed solvent, casting film along with the volatilization of easy volatile solvent, macromolecule precipitation phase film forming, pore-forming, is made polymeric membrane.Here mixed solvent is made up of easy volatile solvent and difficult solvent flashing, and principal item has CAM.
6) macromolecule is made emulsion, this emulsion is evenly distributed in its cloth, again heating make solvent evaporates, gel, crosslinked, be solidified into macromolecular nano filtering membrane.
7) other macromolecular nano filtering film manufacturing method also has interfacial polymerization, monomer catalytic polymerization, plasma polymerization, solution-cast polymerization, water surface expansion etc.
Above macromolecular nano filtering film manufacturing method or be dissolved in macromolecule in the solvent or make emulsion and make film by methods such as curtain coating, coatings, and then heating is except that desolvating, or by under near the macromolecule melting temperature, the crystalline polymer of extruding fast, the high orientation that stretches, or the method by reacting, make various NF membrane.The macromolecular nano filtering membrane manufacturing process complexity that above method is made, the cost height, this has also hindered the more massive of membrane technology and has applied.
Summary of the invention
Purpose of the present invention is exactly to provide in order to overcome the defective that above-mentioned prior art exists that a kind of technology is simple, the manufacture method of lower-cost macromolecular nano filtering membrane.
Purpose of the present invention can be achieved through the following technical solutions: a kind of manufacture method of macromolecular nano filtering membrane, comprise following processing step: the first step, mix, with the nano grade inorganic powder, the mineral powder and the Polyolefin and of nanometer level microporous skeleton structure comprise antioxidant, coupling agent, the processing aid of wetting agent mixes in mixing apparatus, the control temperature is below 50 ℃ in the mixing, the mixing apparatus maximum speed is controlled at 800～1400rpm, it is under 104～110 ℃ of temperature, dry more than 2 hours before the mineral powder of described nano inorganic powder and nanometer micropore skeleton structure mixes; Second the step, extrude, the material that mixes is extruded in double screw extruder, extrusion temperature between 120～240 ℃, the extruder screw back pressure between 5～30MPa, extruder screw rotating speed 50～300 rpm, draw ratio is 20～40; The 3rd step, the calendering film forming, material is extruded feeding through extruder and is given calender, and calender extrudes the film of required thickness, and the rolling mill roller temperature is controlled at 60～130 ℃, and the roller linear velocity is controlled at 5～15m/min; The 4th step, clean, film enters cleaning machine after by moulding, and the difference according to the mixing of materials system in the cleaning machine adds different solvents, if material contains organic oil, then use organic solvent, comprise that cyclohexane, cyclohexanone, acetone, chloroform, trichloro-ethylene do medium, temperature is controlled at solvent boiling point, if the mixing of materials system contains the water-soluble alcohol auxiliary agent, then water is cooked medium, and temperature is controlled at 100 ℃; The 5th step, drying, film carries out drying after cleaning, and baking temperature is controlled at 60～120 ℃.
After described the 5th step, also comprise the 6th step, the 7th step, described the 6th step is hydrophilic treated, it adopts the surfactant solution or the emulsion of concentration 0.05%～5% weight that dried film is carried out hydrophilic treated, described the 7th step is for dry, it carries out drying to the film after cleaning, and baking temperature is 60～120 ℃.
Described antioxidant comprises four, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, thio-2 acid dilaurate, thiobisphenol, described coupling agent comprises vinyl three ('beta '-methoxy ethyoxyl) silane, β-(3,4 epoxycyclohexyls) ethyl trimethoxy silane, three (dodecyl phenylsulfonyloxy) isopropyl titanate, two (dodecyl phosphorous acid acyloxy) four octyloxy titanate esters, described wetting agent comprises neopelex, lauryl sodium sulfate, AEO.
Described double screw extruder extrusion neck ring mold adopts the clothes hanger type, and the Fen Wu district controls temperature respectively, and temperature is at 170～240 ℃.
The roller of described calender is a hollow, but electricity consumption or Steam Heating, roller surface chromium plating, coating is not less than 0.05mm, and roller is withstand voltage to be not less than 2.5KN/cm.
Described cleaning machine used vapour, add the heating of deep fat or electric heater.
The present invention utilizes nano grade inorganic powder and nanometer level microporous skeleton structure powder to be scattered in the vistanex, by mixing, extrude, roll film forming, operations such as cleaning, drying are made the polyolefin NF membrane, pore diameter is at 0.5～1000nm, volumetric porosity 30～70%, hot strength 5～20Mpa, tensile elongation 300～800%.The NF membrane cost of making in this way is low, be beneficial to and apply, and is suitable for large-scale industrialized production.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Material formula is: weight %
Polyethylene or polypropylene 10～80
Nanometer grade calcium carbonate powder (specific area 400m
2/ g) 2～50
Nanometer level microporous precipitated silica powder (specific area 400m
2/ g) 10～80
Four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.2～2.5
Vinyl three ('beta '-methoxy ethyoxyl) silane 0.5～2.5
Neopelex 0.01～0.1
First that wherein nanometer grade calcium carbonate powder and nanometer level microporous precipitated silica powder is following dry 2.5 hours at 105 ℃, then it is added in the high-speed mixer together with other components and mix, mixing temperature is about 40 ℃, and the mixer rotating speed is at 1400rpm.
It is 20 that the material that mixes is put into screw slenderness ratio, and mouthful mould is to extrude in the parallel double-screw extruder of clothes hanger type, and extrusion temperature is at 230 ℃, the extrusion screw rod back pressure is between 30Mpa, extruder screw rotating speed 300rpm, a mouthful mould Fen Wu district controls temperature respectively, and temperature is at 170～240 ℃.
Material feeding after extruder is extruded is given calender, and press mold thickness is 0.20mm, and the calender bowl temperature is 100 ℃, the cylinder linear velocity is 12m/min, the rolling mill roller chrome-faced, and chromium plating thickness is 0.06mm, roller is a hollow, uses Steam Heating, and roller is withstand voltage to be 12KN/cm.
The film that obtains is sent into cleaning machine to be cleaned.
Film after cleaning is carried out drying at 120 ℃.
Dried film is carried out hydrophilic treated with surfactant.
Film after the hydrophilic treated is carried out drying at 100 ℃ again.
The aperture diameter of the membrane material that arrives of process said method is between 50～100nm, and volume porosity is 30%～80%.
Embodiment 2
Process is as embodiment 1, but material formula becomes: weight %
Polyvinyl chloride 10～65
Nanometer grade calcium carbonate powder (specific area 800m
2/ g) 2～50
Nanometer level microporous precipitated silica powder (specific area 800m
2/ g) 10～60
Talcum powder 10～50
Four [3-(3, the 5-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.2～2.5
Vinyl three ('beta '-methoxy ethyoxyl) silane 0.5～2.5
Neopelex 0.01～0.1
The aperture diameter of the membrane material that obtains is between 1～1000nm, and volume porosity is 40%～80%.
Claims (6)
1. the manufacture method of a macromolecular nano filtering membrane, it is characterized in that, comprise following processing step: the first step, mix, the mineral powder and the Polyolefin and of nano grade inorganic powder, nanometer level microporous skeleton structure are comprised that the processing aid of antioxidant, coupling agent, wetting agent mixes in mixing apparatus, the control temperature is below 50 ℃ in the mixing, the mixing apparatus maximum speed is controlled at 800～1400rpm, it is under 104～110 ℃ of temperature, dry more than 2 hours before the mineral powder of described nano inorganic powder and nanometer micropore skeleton structure mixes; Second the step, extrude, the material that mixes is extruded in double screw extruder, extrusion temperature between 120～240 ℃, the extruder screw back pressure between 5～30MPa, extruder screw rotating speed 50～300 rpm, draw ratio is 20～40; The 3rd step, the calendering film forming, material is extruded feeding through extruder and is given calender, and calender extrudes the film of required thickness, and the rolling mill roller temperature is controlled at 60～130 ℃, and the roller linear velocity is controlled at 5～15m/min; The 4th step, clean, film enters cleaning machine after by moulding, and the difference according to the mixing of materials system in the cleaning machine adds different solvents, if material contains organic oil, then use organic solvent, comprise that cyclohexane, cyclohexanone, acetone, chloroform, trichloro-ethylene do medium, temperature is controlled at solvent boiling point, if the mixing of materials system contains the water-soluble alcohol auxiliary agent, then water is cooked medium, and temperature is controlled at 100 ℃; The 5th step, drying, film carries out drying after cleaning, and baking temperature is controlled at 60～120 ℃.
2. the manufacture method of macromolecular nano filtering membrane according to claim 1, it is characterized in that, after described the 5th step, also comprise the 6th step, the 7th step, described the 6th step is hydrophilic treated, and it adopts the surfactant solution or the emulsion of concentration 0.05%～5% weight that dried film is carried out hydrophilic treated, and described the 7th step is for dry, it carries out drying to the film after cleaning, and baking temperature is 60～120 ℃.
3. the manufacture method of macromolecular nano filtering membrane according to claim 1, it is characterized in that, described antioxidant comprises four, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, the thio-2 acid dilaurate, thiobisphenol, described coupling agent comprises vinyl three ('beta '-methoxy ethyoxyl) silane, β-(3,4 epoxycyclohexyls) ethyl trimethoxy silane, three (dodecyl phenylsulfonyloxy) isopropyl titanate, two (dodecyl phosphorous acid acyloxy), four octyloxy titanate esters, described wetting agent comprises neopelex, lauryl sodium sulfate, AEO.
4. the manufacture method of macromolecular nano filtering membrane according to claim 1 is characterized in that, described double screw extruder extrusion neck ring mold adopts the clothes hanger type, and the Fen Wu district controls temperature respectively, and temperature is at 170～240 ℃.
5. the manufacture method of macromolecular nano filtering membrane according to claim 1 is characterized in that, the roller of described calender is a hollow, but electricity consumption or Steam Heating, roller surface chromium plating, coating is not less than 0.05mm, and roller is withstand voltage to be not less than 2.5KN/cm.
6. the manufacture method of macromolecular nano filtering membrane according to claim 1 is characterized in that, described cleaning machine used vapour, adds the heating of deep fat or electric heater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01126384 CN1196519C (en) | 2001-08-01 | 2001-08-01 | Production method of macromolecular nano filtering membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01126384 CN1196519C (en) | 2001-08-01 | 2001-08-01 | Production method of macromolecular nano filtering membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1400038A true CN1400038A (en) | 2003-03-05 |
| CN1196519C CN1196519C (en) | 2005-04-13 |
Family
ID=4666403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01126384 Expired - Fee Related CN1196519C (en) | 2001-08-01 | 2001-08-01 | Production method of macromolecular nano filtering membrane |
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| Country | Link |
|---|---|
| CN (1) | CN1196519C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305779C (en) * | 2004-05-27 | 2007-03-21 | 王世杰 | Method for producing liquid-phase solid film of film filtering tank for sewage treatment |
| CN101601972B (en) * | 2009-07-08 | 2012-05-30 | 宜兴安普克科技有限公司 | Polyethylene ion permeable membrane and preparation method thereof |
| CN105879697A (en) * | 2014-12-16 | 2016-08-24 | 天津工业大学 | Preparation method of environment-protective cellulose-acetate hollow fiber nanofiltration membrane |
-
2001
- 2001-08-01 CN CN 01126384 patent/CN1196519C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305779C (en) * | 2004-05-27 | 2007-03-21 | 王世杰 | Method for producing liquid-phase solid film of film filtering tank for sewage treatment |
| CN101601972B (en) * | 2009-07-08 | 2012-05-30 | 宜兴安普克科技有限公司 | Polyethylene ion permeable membrane and preparation method thereof |
| CN105879697A (en) * | 2014-12-16 | 2016-08-24 | 天津工业大学 | Preparation method of environment-protective cellulose-acetate hollow fiber nanofiltration membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1196519C (en) | 2005-04-13 |
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