CN104084058A - Preparation method of partial crystallized organic macromolecule micropore filtration membrane - Google Patents
Preparation method of partial crystallized organic macromolecule micropore filtration membrane Download PDFInfo
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- CN104084058A CN104084058A CN201410338429.1A CN201410338429A CN104084058A CN 104084058 A CN104084058 A CN 104084058A CN 201410338429 A CN201410338429 A CN 201410338429A CN 104084058 A CN104084058 A CN 104084058A
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Abstract
The invention discloses a preparation method of a partial crystallized organic macromolecule micropore filtration membrane. The preparation method of the partial crystallized organic macromolecule micropore filtration membrane comprises the following steps: a. dissolving partial crystallized organic macromolecule materials into an organic solvent, mixing uniformly, stirring and dissolving to prepare cast membrane liquid; b. stirring the cast membrane liquid obtained from the step a and warming gradually so as to form a homogeneous solution, cooling rapidly to 35 DEG C when the temperature approaches but not exceeds the preset temperature, keeping the temperature constant, stopping stirring when the temperature is reduced to be 35 DEG C, and removing air bubbles generated because of stirring in the cast membrane liquid by a standing method or other methods which cannot result in the evaporation of a solvent in the cast membrane liquid; c. coating by a scraper or an extruding forming method, and blowing by air, thereby generating a primary filtration membrane; and d. finally cleaning a residual organic solvent in the primary filtration membrane by a washing process, and then heating and drying to prepare the micropore filtration membrane. According to the preparation method, micropore filtration membranes with different pore diameters are prepared by utilizing the same cast membrane liquid via a warming/cooling method, so that the manufacturing technology can be simplified.
Description
Technical field
The invention belongs to membrane science technical field, particularly a kind of preparation method of miillpore filter, aperture is at 0.01 ~ 10 micron.
Background technology
Miillpore filter is to utilize macromolecule chemistry material material ﹑ to have molten dose of ﹑ of machine to cause the mixing such as hole agent ﹑ additive, after specially treated, spreads upon on prop carrier and is made.In application of membrane separation technology, miillpore filter is a kind of film kind that range of application is the widest, use simple, quick, be widely used in the various fields such as scientific research, food inspection, chemical industry, nanometer technology, the energy and environmental protection.First generation miillpore filter is mainly by refining nitrocotton, add appropriate cellulose acetate, acetone, n-butanol, ethanol, etc. make, hydrophilic, there is non-toxic sanitary, it is a kind of porous membrane filtration material, the micropore of the more even penetrability of pore-size distribution, microporosity, up to 80% absolute aperture, is mainly used in the filtration of aqueous solution.
The method of manufacturing miillpore filter is a lot, wherein a kind of method is to use phase inversion, this method is to use miillpore filter main material (such as polyether sulfone, polysulfones, cellulose mixture, nylon etc.) to incorporate in organic solvent substantially, add pore-foaming agent and other additives, form casting solution, be then laid on flat board., inject precipitating reagent or via the organic solvent evaporation of casting solution the concentration of casting solution filter membrane main material gradually improved, precipitating until reach its supersaturation thereafter.As for the control of the pore size of miillpore filter, be generally to be decided by quantity and the kind of pore-foaming agent in casting solution.Therefore, the finished film of different pore size need to be with the casting solution of different formulations, and this exists the problem that technique is loaded down with trivial details while just having caused preparing the miillpore filter of different pore size.
Summary of the invention
The object of this invention is to provide a kind of preparation method of partially crystallizable organic polymer miillpore filter, to solve existing different pore size finished film in prior art, need to be with the casting solution of different formulations, while causing preparing the miillpore filter of different pore size, there is the problem that technique is loaded down with trivial details.
For achieving the above object, the present invention is by the following technical solutions:
A preparation method for partially crystallizable organic polymer miillpore filter, is characterized in that: comprise the following steps:
A, partially crystallizable high-molecular organic material is dissolved in organic solvent, evenly mixes, stirring and dissolving is mixed with casting solution;
B, the casting solution that step a is obtained stir and gradually heat up, form homogeneous phase solution, when temperature approaches but is no more than after preset temperature, rapid cooling to 35 DEG C, and keep this temperature-resistant, in the time that temperature is down to 35 DEG C, stop stirring simultaneously, use settled process or other can not cause the method for solvent evaporates in casting solution to be got rid of in casting solution because stirring the bubble producing;
C, the casting solution that utilizes scraper or extrusion moulding that step b is obtained, be evenly laid on glass plate or other level and smooth carriers, then brush the organic solvent evaporation making in casting solution by air, generates nascent filter membrane;
D, finally by crossing water-washing process, clean residual organic solvent in nascent filter membrane, more make miillpore filter through heat drying.
In the raw material of casting solution, according to weight ratio, partially crystallizable high-molecular organic material is 10 ~ 30%, and all the other are organic solvent.
Preferably, described partially crystallizable high-molecular organic material is the one of polyvinylidene fluoride, polyether-ether-ketone, or other organic polymers of similar above-mentioned organic polymer function.
Preferably, described organic solvent is a kind of or two or more mixtures with arbitrary proportion of acetone, dimethylacetylamide, methyl acetate, ethylene glycol, ten fluoronaphthalenes, or other organic solvents of similar above-mentioned solvent function.
In step b, the preset temperature that casting solution heats up is 35 ~ 85 DEG C.
In step b, the rate of temperature fall of rapid cooling to 35 DEG C is to be per minutely not less than 10 DEG C.
The invention has the beneficial effects as follows: utilize partially crystallizable high-molecular organic material, can be subject to temperature impact and change degree of crystallinity.Casting solution is configured to after homogeneous phase solution, heats up rapidly.When reaching after predetermined temperature, then rapid cooling.Utilize the height and the speed of cooling that heat up to control the aperture of finished film.
The advantage of this method is not like traditional miillpore filter that utilizes phase inversion to prepare, and need to prepare with the casting solution of different formulations the finished film of different pore size.This method is to use identical casting solution, prepares the miillpore filter of different pore size through the method for heat up/cooling, flow process that can simplified manufacturing technique.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be further described.
A preparation method for partially crystallizable organic polymer miillpore filter, is characterized in that: comprise the following steps:
A, partially crystallizable high-molecular organic material is dissolved in organic solvent, evenly mixes, stirring and dissolving is mixed with casting solution;
In the raw material of casting solution, according to weight ratio, partially crystallizable high-molecular organic material is 10 ~ 30%, and all the other are organic solvent;
Partially crystallizable high-molecular organic material is the one of polyvinylidene fluoride, polyether-ether-ketone, or other organic polymers of similar above-mentioned organic polymer function;
Organic solvent is a kind of or two or more mixtures with arbitrary proportion of acetone, dimethylacetylamide, methyl acetate, ethylene glycol, ten fluoronaphthalenes, or other organic solvents of similar above-mentioned solvent function;
B, the casting solution that step a is obtained stir and gradually heat up, form homogeneous phase solution, when temperature approaches but is no more than after 35 ~ 85 DEG C, rapid cooling to 35 DEG C, rate of temperature fall is to be per minutely not less than 10 DEG C, and keep this temperature-resistant, and in the time that being down to 35 DEG C, temperature stops stirring simultaneously, and use settled process or other can not cause the method for solvent evaporates in casting solution to be got rid of in casting solution because stirring the bubble producing;
C, the casting solution that utilizes scraper or extrusion moulding that step b is obtained, be evenly laid on glass plate or other level and smooth carriers, then brush the organic solvent evaporation making in casting solution by air, generates nascent filter membrane;
D, finally by crossing water-washing process, clean residual organic solvent in nascent filter membrane, more make miillpore filter through heat drying.
Term definition:
Steam bubble point: the test of steam bubble point is to measure the conventional easy means of the one in miillpore filter aperture.First that filter membrane is fully wetting with suitable liquid when test.As filter membrane be hydrophily conventional pure water is wetting, if be less than 0.1 micron though filter membrane is hydrophobicity or hydrophily aperture, for example ethanol of solvent of conventional low surface tension or isopropyl alcohol are wetting.After filter membrane is wetting, use pressure-air that air is clamp-oned in the hole that in filter membrane, wetted liquid blocks.In the time that air pressure reaches a certain numerical value, the fountain solution in hole can be squeezed out at once.Now liquid can be squeezed to the i.e. steam bubble of the filter membrane point for this reason of the minimum pressure of draining.In principle, filter membrane aperture is larger, and corresponding steam bubble point is lower.In miillpore filter circle, often use bubble point to define the pore size of filter membrane.
Discharge: under quantitative pure water, the filter membrane of unit are, at specified pressure and temperature, pass through the needed time of quantitative pure water.Substantially, millipore water flow is higher, to pass through quantitative pure water required time fewer, the filter membrane percent opening of its demonstration is larger, this term is also by filter membrane circle is commonly used.
Hydrophobicity: refer to a material (hydrophobe) physical property mutually exclusive with water.Lyophobic dust is partial to nonpolar, therefore can be affine with neutrality and non-polar solution (as organic solvent).Lyophobic dust is conventionally converged to one in water, and water can form a very large contact angle and form drops in the time of lyophobic dust surperficial.
Partially crystallizable organic polymer: do not have large side group, other branch or crosslinked polymer, the crystalline plastic viscosity of melting is low, easily flows.Below being cooled to fusing point time, the crystal structure of molecule formation rule, makes its mobility variation.Along with temperature continues to reduce, its degree of crystallinity increases, and intensity also increases, and transparency pool reduces.Crystallization procedure stops at glass transition temperature.Owing to being difficult to obtain 100% crystallization at normal procedure, crystalline plastic presents hypocrystalline conventionally, and it has crystallization and unsetting two kinds of phases simultaneously, and its degree of crystallinity is decided by chemical constitution and the molding condition of polymer.Hemicrystalline plastics have clear and definite fusing point just as ice cube, and glass transition temperature is not obvious, and being usually less than is temperature, and anti-chemistry and heat resistance are good, lubricity is good, hygroscopicity is low, shrinkage factor is high.
embodiment 1
Prepare the hydrophobicity polyvinylidene fluoride miillpore filter of 0.03 micron pore size.
Polyvinylidene fluoride, dimethylacetylamide, methyl acetate, acetone, ethylene glycol are according to the blend at normal temperatures of the ratio of mass ratio 30:35:10:20:5 stirring.After all components is evenly mixed in solvent, reach after 45 DEG C with speed heating direct to the casting solution of 1 DEG C per minute, stop at once heating rapid cooling to 35 DEG C, rate of temperature fall is controlled at and is per minutely not less than 10 DEG C.After casting solution is cooled to 35 DEG C, stop stirring, keep this casting solution to leave standstill at the temperature of 35 DEG C, until casting solution is not containing the bubble producing because of stirring.
After this, utilize scraper or extrusion moulding, the casting solution of 2.5 to 4 millimeters of thickness is evenly laid on glass plate or other level and smooth carriers, then brush by air the high volatility solvent evaporation making in casting solution, generate nascent filter membrane.The nascent filter membrane of semisolid cleans to get rid of contained residual solvent in nascent filter membrane through pure water, more makes finished product filter membrane through heated-air drying.
The filter membrane that the present embodiment is produced is met pure water cannot, by moistening, belong to hydrophobicity filter membrane, but meets the such as ethanol of solvent of low surface tension, can be immediately by moistening, and its ethanol gas bubble point is 45 psi.
embodiment 2
Prepare the hydrophobicity polyvinylidene fluoride miillpore filter of 0.2 micron pore size
Polyvinylidene fluoride, dimethylacetylamide, methyl acetate, acetone, ethylene glycol are according to the blend at normal temperatures of the ratio of mass ratio 24:30:12:30:4 stirring.After all components is evenly mixed in solvent, reach after 60 DEG C with speed heating direct to the casting solution of 1 DEG C per minute, stop at once heating rapid cooling to 35 DEG C, rate of temperature fall is controlled at and is per minutely not less than 10 DEG C.After casting solution is cooled to 35 DEG C, stop stirring, keep this casting solution to leave standstill at the temperature of 35 DEG C, until casting solution is not containing the bubble producing because of stirring.
All the other steps are with embodiment 1.
The filter membrane that the present embodiment is produced is met pure water cannot, by moistening, belong to hydrophobicity filter membrane, but meets the such as ethanol of solvent of low surface tension, can be immediately by moistening, and its ethanol gas bubble point is 18 psi.
embodiment 3
Prepare the hydrophobicity polyvinylidene fluoride miillpore filter of 0.8 micron pore size.
Polyvinylidene fluoride, dimethylacetylamide, methyl acetate are according to the blend at normal temperatures of the ratio of mass ratio 18:50:32 stirring.After all components is evenly mixed in solvent, reach after 70 DEG C with speed heating direct to the casting solution of 1 DEG C per minute, stop at once heating rapid cooling to 35 DEG C, rate of temperature fall is controlled at and is per minutely not less than 10 DEG C.After casting solution is cooled to 35 DEG C, stop stirring, keep this casting solution to leave standstill at the temperature of 35 DEG C, until casting solution is not containing the bubble producing because of stirring.
All the other steps are with embodiment 1.
The filter membrane that the present embodiment is produced is met pure water cannot, by moistening, belong to hydrophobicity filter membrane, but meets the such as ethanol of solvent of low surface tension, can be immediately by moistening, and its ethanol gas bubble point is 7 psi.
Claims (7)
1. a preparation method for partially crystallizable organic polymer miillpore filter, is characterized in that: comprise the following steps:
A, partially crystallizable high-molecular organic material is dissolved in organic solvent, evenly mixes, stirring and dissolving is mixed with casting solution;
B, the casting solution that step a is obtained stir and gradually heat up, form homogeneous phase solution, when temperature approaches but is no more than after preset temperature, rapid cooling to 35 DEG C, and keep this temperature-resistant, in the time that temperature is down to 35 DEG C, stop stirring simultaneously, use settled process or other can not cause the method for solvent evaporates in casting solution to be got rid of in casting solution because stirring the bubble producing;
C, the casting solution that utilizes scraper or extrusion moulding that step b is obtained, be evenly laid on glass plate or other level and smooth carriers, then brush the organic solvent evaporation making in casting solution by air, generates nascent filter membrane;
D, finally by crossing water-washing process, clean residual organic solvent in nascent filter membrane, more make miillpore filter through heat drying.
2. the preparation method of partially crystallizable organic polymer miillpore filter as claimed in claim 1, is characterized in that: in the raw material of casting solution, according to weight ratio, partially crystallizable high-molecular organic material is 10 ~ 30%, and all the other are organic solvent.
3. the preparation method of partially crystallizable organic polymer miillpore filter as claimed in claim 1 or 2, it is characterized in that: described partially crystallizable high-molecular organic material is the one of polyvinylidene fluoride, polyether-ether-ketone, or other organic polymers of similar above-mentioned organic polymer function.
4. the preparation method of partially crystallizable organic polymer miillpore filter as claimed in claim 1, it is characterized in that: described organic solvent is a kind of or two or more mixtures with arbitrary proportion of acetone, dimethylacetylamide, methyl acetate, ethylene glycol, ten fluoronaphthalenes, or other organic solvents of similar above-mentioned solvent function.
5. the preparation method of partially crystallizable organic polymer miillpore filter as claimed in claim 1, is characterized in that: in step b, the preset temperature that casting solution casting solution heats up is 35 ~ 85 DEG C.
6. the preparation method of partially crystallizable organic polymer miillpore filter as claimed in claim 1, is characterized in that: in step b, the rate of temperature fall of rapid cooling to 35 DEG C is to be per minutely not less than 10 DEG C.
7. the preparation method of partially crystallizable organic polymer miillpore filter as claimed in claim 1, is characterized in that: in step b, heating rate is less than 1 DEG C per minute.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030032686A1 (en) * | 1998-01-29 | 2003-02-13 | Rebecca Klotzer | Expanded porous thermoplastic polymer membranes |
| CN101234300A (en) * | 2007-02-01 | 2008-08-06 | 中国科学院化学研究所 | Method for preparing polyvinylidene fluoride microporous filtering film |
| CN103055724A (en) * | 2011-10-19 | 2013-04-24 | 华东理工大学 | Method for preparing polysulfones polymer microporous membrane by counter-current thermally induced phase separation method |
| CN103372380A (en) * | 2012-04-28 | 2013-10-30 | 亚美滤膜（南通）有限公司 | Preparation method of hydrophobic polyvinylidene difluoride microporous filter membrane |
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- 2014-07-16 CN CN201410338429.1A patent/CN104084058A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030032686A1 (en) * | 1998-01-29 | 2003-02-13 | Rebecca Klotzer | Expanded porous thermoplastic polymer membranes |
| CN101234300A (en) * | 2007-02-01 | 2008-08-06 | 中国科学院化学研究所 | Method for preparing polyvinylidene fluoride microporous filtering film |
| CN103055724A (en) * | 2011-10-19 | 2013-04-24 | 华东理工大学 | Method for preparing polysulfones polymer microporous membrane by counter-current thermally induced phase separation method |
| CN103372380A (en) * | 2012-04-28 | 2013-10-30 | 亚美滤膜（南通）有限公司 | Preparation method of hydrophobic polyvinylidene difluoride microporous filter membrane |
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Application publication date: 20141008 |