CN101874992B - PVDF (Polyvinylidene Fluoride) alloy film containing two hydrophilic high polymers and preparation method - Google Patents
PVDF (Polyvinylidene Fluoride) alloy film containing two hydrophilic high polymers and preparation method Download PDFInfo
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- CN101874992B CN101874992B CN201010153232.2A CN201010153232A CN101874992B CN 101874992 B CN101874992 B CN 101874992B CN 201010153232 A CN201010153232 A CN 201010153232A CN 101874992 B CN101874992 B CN 101874992B
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Abstract
The invention relates to a PVDF (Polyvinylidene Fluoride) porous hollow fibrous film and a preparation method thereof. In a formula, the prepared film comprises the following components in mass percentage: 25-45 percent of first polymer P1: PVDF, 0-4.5 percent of second polymer P2: polymethyl methacrylate (PMMA), 0.5-5 percent of third polymer P3: polyvinylpyrrolidone (PVP), 25-35 percent of first thinner D1: dimethylsulfoxide and 22-38 percent of second thinner D2: triglycol. The PVDF hollow fibrous ultrafiltration and microfiltration film prepared by adopting the method is the hollow fibrous film with excellent chemical stability and high pollution resistance and strength and can supply high-performance film products for an MBR (Membrane Bio-Reactor) process.
Description
Technical field
The present invention relates to a kind of Kynoar (PVDF) porous hollow fiber membrane and method for making thereof, especially relate to a kind of Kynoar (PVDF) porous hollow fiber membrane and the method for making thereof that contain two kinds of hydrophilic high polymers.
Background technology
Membrane biological reactor process (MBR) is a kind of novel, efficient sewage disposal technology, and it can realize being separated of biocatalytic reaction and water and degradation material simultaneously, water resource is regenerated, realizes reuse water standard.Sewage advanced treatment and the regeneration new technology of advanced, efficient and low energy consumption in the present age.Wherein preparing that intensity is high, antifouling property good, the milipore filter of low cost and microfiltration membranes, is the core technology of membrane biological reactor process.But at present most ofs commercially to surpass, microfiltration membranes effect is all undesirable, industrial requirement cannot be met.On the other hand, at present super, microfiltration membranes most employing phase separation legal system is standby, the film made comprises the large cavity structure of finger-like mostly, membrane aperture skewness, intensity difference, in sewage, use easy fracture of wire, membrane lifetime is short, is unsuitable for applying in membrane biological reactor process.
Summary of the invention
The object of the invention is propose a kind of be suitable for applying in membrane biological reactor process Kynoar porous hollow fiber membrane and method for making.
Kynoar porous hollow fiber membrane provided by the invention, the Formulation Ingredients of its masking and content thereof by percentage to the quality:
First polymer P
1: Kynoar (PVDF) 25 ~ 45%
Second polymer P
2: polymethyl methacrylate (PMMA) 0 ~ 4.5%
Terpolymer P
3: polyvinylpyrrolidone (PVP) 0.5 ~ 5%
First diluent D
1: methyl-sulfoxide 25 ~ 35%
Second diluent D
2: triethylene glycol 22 ~ 38%.
Preferably, wherein the mass ratio of each composition is:
P
2/P
1＝0～0.18，
P
3/P
1＝0.02～0.11，
D
1/D
2＝4/5～6/5，
P/ (P+D)=(25 ~ 45) %, wherein: P=P
1+ P
2+ P
3, D=D
1+ D
2
Wherein P+D is absolutely.
Preferred, wherein the mass ratio of each composition is:
Wherein said P
2/ P
1=0.04 ~ 0.10,
Wherein said P
3/ P
1=0.04 ~ 0.07,
Wherein said D
1/ D
2=8/9 ~ 1/1,
Wherein said P/ (P+D)=(30 ~ 35) %.
Preferably, add nucleant agent N in first, second mixing diluents solvent described: benzylalcohol, and the addition of nucleator (mass ratio) is N/P
1=4 ‰.
Preferably, wherein said Kynoar (PVDF) weight average molecular weight is 300000, described polymethyl methacrylate (PMMA) weight average molecular weight is 70000, and described polyvinylpyrrolidone (PVP) viscosity average molecular weigh is 130000.
On the other hand, present invention also offers a kind of preparation method of described hollow-fibre membrane, comprise the following steps: the pretreatment of (1) polymeric material
Kynoar, polymethyl methacrylate, polyvinylpyrrolidone are carried out drying in dryer, and bake out temperature is 50 ~ 80 DEG C;
(2) preparation of masking blend raw material
By Kynoar P
1, polymethyl methacrylate P
2with polyvinylpyrrolidone P
3, methyl-sulfoxide D
1with triethylene glycol D
2after weighing in proportion, be first placed in stirred tank, at the temperature of 120 ~ 150 DEG C, carry out stirring and dissolving, mixing time is 15 ~ 25 hours, speed of agitator is 80 ~ 120 revs/min, by the masking Polymer Solution cooling granulation be in atmosphere uniformly dissolved, obtains blend raw material;
(3) the extruding of hollow-fibre membrane, be shaped
(4) diluent leaching
Immersed in reverse osmosis water by the doughnut intermediate made, remove the diluent mixture in film, water temperature is 18 ~ 35 DEG C, and leaching time is 3 ~ 6 hours;
(5) dry
The hollow-fibre membrane made at room temperature is dried and obtains doughnut membrane product.
Preferably, the temperature wherein in step (1) is 60 ~ 70 DEG C.
Preferably, wherein the mixing time described in step (2) is 22 ~ 24 hours, and described speed of agitator is 90 ~ 100 revs/min.
Preferably, wherein step (3) comprises the following steps:
(3-1) above-mentioned blend raw material is added in double screw extruder melt extrude;
(3-2) melt blended material extruded, through filter and spinning pump, is extruded from doughnut annular die, forms the as-spun fibre of hollow;
(3-3) above-mentioned as-spun fibre is lowered the temperature in atmosphere, then cooling curing in cooling fluid, through winder rolling, make doughnut intermediate.
Preferred, wherein the charging rate of step (3-1) Raw is 8kg/h, and extruder is divided into 8 sections to heat along spiro rod length direction, the temperature range of 8 sections is 100 ~ 150 DEG C, and screw speed is 120 revs/min.
Preferred, wherein in step (3-2), the external diameter of annular die single hole is 5.5 millimeters (mm), and internal diameter is 5.0 millimeters, and temperature is 130 ~ 140 DEG C, annular die centre bore passes into nitrogen, and the pressure of nitrogen is 10 ~ 30 millimeter of water (mmH
2o), preferred nitrogen pressure is 15 ~ 25 millimeter of water (mmH
2o).
Preferred, be wherein lower the temperature in the air of 5 ~ 25 DEG C in temperature by above-mentioned as-spun fibre in step (3-3), preferred air themperature 10 ~ 15 DEG C, winder rolling speed is 10 ~ 15m/min, and cooling fluid is methyl-sulfoxide C
1, triethylene glycol C
2, and water C
3the mixed liquor of three, coolant temperature is 10 ~ 30 DEG C, and the temperature of preferred described cooling fluid is 15 ~ 20 DEG C.
Preferred, wherein export to from mouth mould the air gap cooling liquid level and remain 5 ~ 25 centimetres, preferred the air gap is 10 ~ 20 centimetres.
Preferably, the ratio of wherein three's mixing is (mass ratio): (C
1+ C
2)/C
3=1.4/1 ~ 3/1, C
1/ C
2=4/5 ~ 6/5.
Preferred, (C
1+ C
2)/C
3=2/1 ~ 2.5/1, C
1/ C
2=8/9 ~ 1/1.
Preferably, wherein the water temperature described in step (4) is 20 ~ 30 DEG C, and the time is 4 ~ 5 hours.
The Kynoar (PVDF) that the present invention adopts has outstanding solvent resistant, acid and alkali-resistance, resistance to oxidation, the characteristic such as weather-proof, there are excellent heat resistance and toughness, fluorine element particularly in material has stronger negative polarity, makes PVDF not easily be adsorbed with organic pollutants, shows good anti pollution property, is the preferred material of MBR technique.
But because PVDF material hydrophobic is strong, surface energy is low, has repulsive interaction to hydrone, and the present invention adopts at least one hydrophilic high molecular material blended with it, thus effectively improves the hydrophily of pvdf membrane.
On this basis, the present invention also proposes a kind of new mixed diluent system, this system is made up of two component mixed solvents, one of them component is solvent or the cosolvent of polymer, another component is the non-solvent of polymer, by different proportion therebetween in adjustment mixed diluent, carry out interactional power between telomerized polymer and diluent, and then change the phase-separated state of polymer/diluent system, reach the object of regulation and control membrane pore structure, the film of the required three-dimensional net structure of preparation.
On this basis, the present invention adopts the mixed liquor of diluent and water as cooling fluid, by changing composition and the temperature of cooling fluid, regulate the aperture on film surface and the size of percent opening, the PVDF that preparation has hole density gradient is super, microfiltration membranes, improve film to pollutant retain characteristic and anti-soil blocks up ability.
On the other hand, preparation method provided by the invention, make use of the principle of " high-temperature digestion, low temperature phase-splitting ", by polymer and diluent at high temperature mixed dissolution uniformly Casting solution, then after solution is made tabular, tubulose and hollow fiber, through cooling, cooling, casting solution system generation liquid-liquid or solid-liquid phase are separated, after polymeric system solidification, then by diluent extraction removing, namely obtain porous diffusion barrier.The method is extensive to the adaptability of high polymer material, is not only suitable for conventional high polymer, be also suitable for dissolved solution poor, even due to highly crystalline, undissolvable polymer under common normal temperature.Because film-forming temperature is relatively high, the concentration of corresponding filming polymer is also relatively high, the large cavity structure of that finger-like occurring that phase separation method is made can be avoided, make pore structure even, highly through three-dimensional net structure, therefore film strength is high, can adapt to the requirement of MBR technique.The PVDF doughnut adopting the present invention to prepare is super, microfiltration membranes, has excellent chemical stability, the hollow-fibre membrane that antipollution, intensity are high, can provide high performance film product for MBR technique.
In addition, in traditional filming technology, diluent is non-water-soluble, film be shaped after need adopt alcohol, ketone, based organic solvent as extractant, this technique except with an organic solvent itself costly except, also to add the cost reclaiming extractant, the discharge of organic pollution can't be avoided.Because two components in mixed diluent system are water miscible in the present invention, so just can adopt water as extractant to extract the diluent (cosolvent) in membrane, the trouble adopting organic solvent to bring as extractant can be avoided, also can reduce the manufacturing cost of film.
Hollow-fibre membrane external diameter of the present invention is 1.2 ~ 1.3 millimeters, wall thickness is 270 ~ 300 nanometers, membrane pore structure is three-dimensional interpenetrating polymer network structure (see accompanying drawing 1), film section is asymmetric, and film outmost surface aperture is minimum, and fascia edge hole is fine and close, aperture is less, aperture increases gradually from outside to inside, and inner surface aperture is maximum, is a kind of super, microfiltration membranes with density gradient pores section structure.The chemically-resistant cleaning that super, microfiltration membranes of the present invention has had and hydrophily, intensity is high, flux is large, good toughness, has excellent contamination resistance, is adapted at most using in MBR.City domestic sewage, industrial wastewater can be carried out advanced treating, reach Treated sewage reusing water standard.Compared with traditional Wastewater Treated by Activated Sludge Process waste water, treatment effeciency improves more than 3 times, and effluent quality is good, and Chemical Oxygen Demand in Wastwater (COD) clearance is greater than 98%, ammonia-nitrogen removal efficiency is high, and treatment facility is compact, take up an area less, automaticity is high, convenient operation and management.
Accompanying drawing explanation
The electron scanning micrograph figure of Fig. 1 film section.
Detailed description of the invention
For a more detailed description to the present invention below in conjunction with embodiment, but described embodiment is not construed as limiting the invention.
Embodiment 1
Percent mass be 35% PVDF, mass percent be 3.5% polymethyl methacrylate and mass percent be the polymer blend of the oven dry resin composition of the polyvinylpyrrolidone of 1.4%, and 0.14% benzylalcohol join methyl-sulfoxide and triethylene glycol composition mixed solvent in, wherein the percent mass of methyl-sulfoxide is 32.5%, and the percent mass of triethylene glycol is 27.6%.Joined by said mixture in stirred tank, carry out stirring and dissolving after 24 hours at the temperature of 150 DEG C, rotating speed under being 120 revs/min of kind conditions, cooling granulation in atmosphere, obtains blended material.With the charging rate of 8kg/h, preprepared blend composition is joined in double screw extruder.The temperature in extruder 1-8 district is respectively 100 DEG C, 115 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 140 DEG C, and screw speed is 120 revs/min.After mixed material melt extrudes in dual-screw-stem machine, enter four orifice ring shape die extrusions, make hollow as-spun fibre by filter and spinning pump, mouth mould single hole external diameter is 5.5mm, and internal diameter is 5mm, and temperature is 140 DEG C, and it is 15mmH that mouth mould centre bore passes into pressure
2the N of O
2gas.As-spun fibre is in the air of 15 DEG C in temperature, and idling stopping distance (the air gap) is 20cm, enters into cooling fluid cooling curing, with the speed rolling of 15m/min.Wherein contain 28.6% water in cooling fluid, the triethylene glycol of 35.7%, the methyl-sulfoxide of 35.7%, the temperature of cooling fluid is 20 DEG C.Preformed hollow-fibre membrane, in the reverse osmosis water of 30 DEG C, leaches and at room temperature dries after 5 hours, make doughnut membrane product of the present invention.By scanning electronic microscope observation, the inierpeneirating network structure of the section of film, asymmetric milipore filter, film surface average pore size is 42 nanometers (nm), and fiber outer diameter is 1.3 millimeters (mm), and wall thickness is 300 microns (μm).Temperature be 25 DEG C, under 0.1MPa pressure, pure water flux is 560L/m
2h, tensile strength of fiber is 7.1MPa, elongation at break 47%.
Main preparation process condition and the film properties of embodiment of the present invention 2-5 is provided below in conjunction with table 1, but the content of each composition of the present invention is not limited to listed numerical value in this table, for a person skilled in the art, reasonable generalization and reasoning can be carried out in the basis of number range listed by table completely, and it should be noted that, although listed file names with some other parameter in table 1, this this Parameter Conditions has been described as necessary condition.For the present invention, the content of core is to improve film formula of liquid, and therefore, other parameters listed file names with in table 1 are just in order to provide about technical information of the present invention in more detail, be all preferred condition, described as necessary condition of the present invention.
The formulation ratio of table 1: embodiment 2-5, main preparation process condition and film properties
Wherein, film properties data relevant in table 1 are after hollow-fibre membrane is cooled brittle failure in liquid nitrogen, and use the section of stereomicroscope to described film take a picture and measure, method is as follows:
(1) Micro-Structure Analysis of film
Sample is made in film brittle failure in liquid nitrogen, sample is fixed on sample stage, under the voltage of 30KV, adopt SEM (QuanTa 200FEG) to observe film section and surface texture.
(2) film-strength test
Film is made sample silk, two ends medical proof fabric is reinforced.Universal testing machine carries out stretch (GT-TS-2000, GOTECHCO, Taiwan), the hot strength of test membrane silk and elongation at break.
(3) the pure water flux test of film
Testing arrangement is by external-compression type ultrafilter, N
2gas cylinder, vacuum tank form, and hollow-fibre membrane epoxide-resin glue is packaged into test sample, and employing temperature is the deionized water of 25 DEG C, tests under the pressure of 0.1MPa.
Pure water flux be defined as unit interval under the test conditions above, per membrane area through pure water quality.
That is: J=W/AT
Wherein, J is pure water flux (kg/m
2h), A is the external surface area (m of film
2), W is the permeable amount (kg) of film, and T is the testing time (h).
(4) mensuration of the external diameter of hollow-fibre membrane, internal diameter and wall thickness
Any corresponding improvement carried out on basis of the present invention, does not all depart from thought of the present invention, all falls into the scope of protection of the invention.
Claims (16)
1. a hollow-fibre membrane, is characterized in that the formula of masking and content thereof are by percentage to the quality:
The mass ratio of wherein said each composition is:
P
2/P
1＝0～0.18，
P
3/P
1＝0.02～0.11，
D
1/D
2＝4/5～6/5，
P/ (P+D)=(25 ~ 45) %, wherein: P=P
1+ P
2+ P
3, D=D
1+ D
2
Wherein P+D is absolutely;
Add nucleant agent N in first, second wherein said mixing diluents solvent: benzylalcohol, and the quality that adds of nucleator is made a gesture of measuring as N/P
1=4 ‰;
Wherein said Kynoar (PVDF) weight average molecular weight is 300000, described polymethyl methacrylate (PMMA) weight average molecular weight is 70000, and described polyvinylpyrrolidone (PVP) viscosity average molecular weigh is 130000.
2. hollow-fibre membrane as claimed in claim 1, is characterized in that the mass ratio of wherein each composition is:
Wherein said P
2/ P
1=0.04 ~ 0.10,
Wherein said P
3/ P
1=0.04 ~ 0.07,
Wherein said D
1/ D
2=8/9 ~ 1/1,
Wherein said P/ (P+D)=(30 ~ 35) %.
3. prepare a preparation method for hollow-fibre membrane as claimed in claim 1, it is characterized in that this preparation method comprises the following steps:
(1) pretreatment of polymeric material: Kynoar, polymethyl methacrylate, polyvinylpyrrolidone are carried out drying in dryer, bake out temperature is 50 ~ 80 DEG C;
(2) preparation of masking blend raw material: by Kynoar P
1, polymethyl methacrylate P
2with polyvinylpyrrolidone P
3, methyl-sulfoxide D
1with triethylene glycol D
2after weighing in proportion, be first placed in stirred tank, at the temperature of 120 ~ 150 DEG C, carry out stirring and dissolving, mixing time is 15 ~ 25 hours, speed of agitator is 80 ~ 120 revs/min, by the masking Polymer Solution cooling granulation be in atmosphere uniformly dissolved, obtains blend raw material;
(3) the extruding of hollow-fibre membrane, be shaped;
(4) diluent leaching: immersed in reverse osmosis water by the doughnut intermediate made, remove the diluent mixture in film, water temperature is 18 ~ 35 DEG C, and leaching time is 3 ~ 6 hours;
(5) dry: the hollow-fibre membrane made at room temperature is dried and obtains doughnut membrane product.
4. preparation method as claimed in claim 3, is characterized in that the temperature in described step (1) is 60 ~ 70 DEG C.
5. preparation method as claimed in claim 3, it is characterized in that the mixing time in described step (2) is 22 ~ 24 hours, described speed of agitator is 90 ~ 100 revs/min.
6. preparation method as claimed in claim 3, is characterized in that described step (3) comprises the following steps:
(3-1) above-mentioned blend raw material is added in double screw extruder melt extrude;
(3-2) melt blended material extruded, through filter and spinning pump, is extruded from doughnut annular die, forms the as-spun fibre of hollow;
(3-3) above-mentioned as-spun fibre is lowered the temperature in atmosphere, then cooling curing in cooling fluid, through winder rolling, make doughnut intermediate.
7. preparation method as claimed in claim 6, the charging rate that it is characterized in that described step (3-1) Raw is 8kg/h, extruder is divided into 8 sections to heat along spiro rod length direction, the temperature range of 8 sections is 100 ~ 150 DEG C, and screw speed is 120 revs/min.
8. preparation method as claimed in claim 6, it is characterized in that the external diameter of annular die single hole is 5.5 millimeters in described step (3-2), internal diameter is 5.0 millimeters, and temperature is 130 ~ 140 DEG C, annular die centre bore passes into nitrogen, and the pressure of nitrogen is 10 ~ 30 millimeters of water.
9. preparation method as claimed in claim 8, is characterized in that described nitrogen pressure is 15 ~ 25 millimeters of water.
10. preparation method as claimed in claim 6, it is characterized in that being lower the temperature in the air of 5 ~ 25 DEG C in temperature by above-mentioned as-spun fibre in described step (3-3), winder rolling speed is 10 ~ 15m/min, and cooling fluid is methyl-sulfoxide C
1, triethylene glycol C
2, and water C
3the mixed liquor of three, coolant temperature is 10 ~ 30 DEG C.
11. preparation methods as claimed in claim 10, is characterized in that the temperature of described cooling fluid is 15 ~ 20 DEG C.
12. preparation methods as claimed in claim 6, wherein export to from mouth mould the air gap cooling liquid level and remain 5 ~ 25 centimetres.
13. preparation methods as claimed in claim 12, is characterized in that described the air gap is 10 ~ 20 centimetres.
14. preparation methods as claimed in claim 10, is characterized in that the mass ratio of three's mixing in described cooling fluid is: (C
1+ C
2)/C
3=1.4/1 ~ 3/1, C
1/ C
2=4/5 ~ 6/5.
15. preparation methods as claimed in claim 14, is characterized in that the mass ratio of three's mixing in wherein said cooling fluid is: (C
1+ C
2)/C
3=2/1 ~ 2.5/1, C
1/ C
2=8/9 ~ 1/1.
16. preparation methods as claimed in claim 3, it is characterized in that the described water temperature described in step (4) is 20 ~ 30 DEG C, the time is 4 ~ 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010153232.2A CN101874992B (en) | 2010-04-23 | 2010-04-23 | PVDF (Polyvinylidene Fluoride) alloy film containing two hydrophilic high polymers and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010153232.2A CN101874992B (en) | 2010-04-23 | 2010-04-23 | PVDF (Polyvinylidene Fluoride) alloy film containing two hydrophilic high polymers and preparation method |
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| CN101874992B true CN101874992B (en) | 2015-06-24 |
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ID=43017735
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| KR102006324B1 (en) | 2013-01-21 | 2019-08-01 | 주식회사 엘지화학 | Continuous Process of Preparing Hydrophilic Hollow Fiber Using Extruder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| CN101239280A (en) * | 2007-11-27 | 2008-08-13 | 北京市射线应用研究中心 | Reinforced microporous filter membrane and method and device for preparing the same |
| CN101357303A (en) * | 2008-09-25 | 2009-02-04 | 杭州洁弗膜技术有限公司 | Preparation method of polyvinylidene fluoride hollow fiber composite microporous film with strong interface binding power |
| CN101507902A (en) * | 2009-02-19 | 2009-08-19 | 苏州膜华材料科技有限公司 | Preparation method of porous polyvinylidene fluoride alloy membrane for treating and recycling waste water |
-
2010
- 2010-04-23 CN CN201010153232.2A patent/CN101874992B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| CN101239280A (en) * | 2007-11-27 | 2008-08-13 | 北京市射线应用研究中心 | Reinforced microporous filter membrane and method and device for preparing the same |
| CN101357303A (en) * | 2008-09-25 | 2009-02-04 | 杭州洁弗膜技术有限公司 | Preparation method of polyvinylidene fluoride hollow fiber composite microporous film with strong interface binding power |
| CN101507902A (en) * | 2009-02-19 | 2009-08-19 | 苏州膜华材料科技有限公司 | Preparation method of porous polyvinylidene fluoride alloy membrane for treating and recycling waste water |
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