CN102784563B - High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method - Google Patents
High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method Download PDFInfo
- Publication number
- CN102784563B CN102784563B CN201110127999.2A CN201110127999A CN102784563B CN 102784563 B CN102784563 B CN 102784563B CN 201110127999 A CN201110127999 A CN 201110127999A CN 102784563 B CN102784563 B CN 102784563B
- Authority
- CN
- China
- Prior art keywords
- corvic
- polyvinyl chloride
- hollow fiber
- stirred tank
- casting solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a high-strength hollow fiber hollow fiber ultrafilter membrane and its preparation method to overcome defects of low strength and bad stability of present polyvinyl chloride ultrafilter membranes. The high-strength polyvinyl chloride hollow fiber ultrafilter membrane disclosed in the invention is prepared from the following components: 12-21wt% of a polyvinyl chloride resin, 2-10wt% of a hydrophilic resin, 1-9wt% of an additive, and the balance a solvent, wherein the polyvinyl chloride resin is formed through combining two polyvinyl chloride resins with the K values being 60-90, and concretely comprises 50-90wt% of the polyvinyl chloride resin having a lower K value, and the balance the polyvinyl chloride resin having a higher K value. The substantial strength improvement and the stable performances of the hollow fiber ultrafilter membrane are realized through mutually winding and connecting polyvinyl chloride having different chain lengths in the invention.
Description
Technical field
The present invention relates to milipore filter production technical field, particularly a kind of high intensity PVC hollow fiber hyperfiltration and preparation method thereof.
Background technology
Society water resource is day by day in short supply, and natural water and reuse water purification are the Vital Strategic Problems being related to national economy.In various process for purifying water, ultrafiltration is low with its good purification, energy consumption, it is little to take up an area, be easy to the advantage such as modularization, easy cleaning recovery is taken seriously gradually.
Conventional milipore filter material comprises cellulose acetate (CA), polysulfones (CS), polyether sulfone (PES), polypropylene fine (PAN), Kynoar (PVDF), polyvinyl chloride (PVC) etc.In various material, PVC is attractive with advantages such as its cheapness, chemically-resistant pollutions, but common single PVC material is crisp, the lateral impact forces tolerated and longitudinal stretching force limited, this limit to a certain extent its application.
Pvc Ultrafiltration Membrane wants energy large-scale application, to adapt to various complicated water quality and can tolerate water impact and positive backwash frequently, then must strengthen modification to it.And mention that the document strengthened PVC hollow fiber ultrafiltration membrane is little at present.A kind of high intensity PVC hollow fiber hyperfiltration of the disclosure of the invention of publication number CN101254422A, this PVC hollow fiber ultrafiltration membrane anti-impact resin (methyl methacrylate, butadiene, cinnamic terpolymer, MBS) blended polyvinyl chloride is to improve its impact strength, but the lasting compatibility of impact resins and polyvinyl chloride is difficult to ensure, the PVC hollow fiber ultrafiltration membrane unstable properties of production.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of high intensity PVC hollow fiber hyperfiltration, it utilizes the polyvinyl chloride of different chain length to be mutually intertwined and connected, and significantly improves hollow fiber ultrafiltration membrane intensity and stable performance.
Present invention also offers the preparation method of this PVC hollow fiber ultrafiltration membrane, technique is simple, production cost is low.
The technical solution adopted for the present invention to solve the technical problems is: a kind of high intensity PVC hollow fiber hyperfiltration, the casting solution that described high intensity PVC hollow fiber hyperfiltration is made up of following component is by weight percentage made: Corvic 12 ~ 21%, hydrophilic resin 2 ~ 10%, additive 1 ~ 9%, surplus is solvent, described Corvic is that in the Corvic of 60 ~ 90 two kinds combine by K value, in the Corvic of two kinds of K values by weight: the Corvic that K value is low is 50 ~ 90%, surplus is the Corvic that K value is high.
K value be 60 ~ 90 Corvic refer to that commercially available K value is the Corvic of 60 ~ 90, K value is that measuring of average degree of polymerization (refers to the characterizing method-viscosity of Corvic molecular weight, viscosity number, the degree of polymerization and K value, Jiang Wanan, " polyvinyl chloride " the 3rd phase in 1989), the Corvic of different K values then has different molecular weight, the present invention adopts the polyvinyl chloride of different molecular weight rank, and to strengthen hollow fiber ultrafiltration membrane, (principle is utilize the polymer of different chain length to be mutually intertwined and connected, significantly improve hollow fiber ultrafiltration membrane intensity), avoid with the blended chemical property difference of different materials and consistency problem, .Adopt general rigidity and toughness after the polyvinyl chloride film forming of single lower molecular weight all poor, and adopt its solute effect of the polyvinyl chloride of single higher molecular weight poor, high-temperature digestion can cause again the degraded of polyvinyl chloride.The present invention do not introduce new substance classes and do not add loaded down with trivial details technique prerequisite under, realize the enhancing of PVC hollow fiber ultrafiltration membrane.
As preferably, described hydrophilic resin is the bipolymer of Styrene And Chloroalkyl Acrylates, and the bipolymer of described Styrene And Chloroalkyl Acrylates is formed by the styrene of 60 ~ 90% and the acroleic acid polymerization of 10 ~ 40% by weight.
As preferably, described additive is polyvinyl alcohol.Polyvinyl alcohol mainly plays perforating action.
As preferably, described solvent be dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE one.The preferred 1-METHYLPYRROLIDONE of solvent.
A preparation method for high intensity PVC hollow fiber hyperfiltration, described preparation method's step is as follows:
(1) solvent is added in stirred tank, add in stirred tank after again the Corvic of two kinds of K values being mixed in proportion, stir, after Corvic is swelling, add hydrophilic resin, be uniformly mixed, doping in the most backward stirred tank, continues stirring 5 ~ 10 hours, obtained casting solution, in whole process, the temperature of stirred tank controls at 40 ~ 80 DEG C;
(2), by casting solution standing and defoaming 2 ~ 4 hours, then casting solution is extruded by spinning head, enter coagulating bath, phase-splitting film forming; Coagulating bath China and foreign countries lime set is 10 ~ 50 DEG C of water, interior lime set during film forming to be mass concentration be 3 ~ 25% calcium chloride water, temperature controls at 12 ~ 18 DEG C.
The present invention is by configuring the aqueous solution (calcium chloride) of inorganic salts as interior coagulating bath, and the concentration of coagulating bath in controlling and temperature, a regulation and control point phase velocity, obtains spongiform network hole, macropore in minimizing film, thus realizes strengthening.The present invention adopts dry-wet process film, casting solution in atmosphere vertically downward travel distance be 0 ~ 40cm, spinning temperature 40 ~ 80 DEG C, spinning speed 20 ~ 60m/min.
The invention has the beneficial effects as follows: utilize the polyvinyl chloride of different chain length to be mutually intertwined and connected, significantly improve hollow fiber ultrafiltration membrane intensity and stable performance; By configuring the aqueous solution of inorganic salts as interior coagulating bath, and the concentration of coagulating bath in controlling and temperature, regulation and control point phase velocity, obtains spongiform network hole, reduces macropore in film, thus realizes strengthening.
Accompanying drawing explanation
Fig. 1 is the partial view of the polyvinyl chloride hollow fiber cross section that embodiment 1 obtains.
Detailed description of the invention
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment 1:
(1) 1-METHYLPYRROLIDONE 72kg is added in stirred tank, add in stirred tank after again the Corvic 4.8kg of the Corvic 11.2kg of K value 65 and K value 85 being mixed, stir, after Corvic is swelling, add the bipolymer copolymerization ratio 72:28 of the bipolymer 4kg(Styrene And Chloroalkyl Acrylates of Styrene And Chloroalkyl Acrylates), be uniformly mixed, Polyvinyl alcohol 8kg in the most backward stirred tank, continue stirring 8 hours, obtained casting solution, in whole process, the temperature of stirred tank controls at 66 DEG C;
(2) by casting solution standing and defoaming 3 hours, the present invention adopts dry-wet process film: the casting solution after deaeration is got to spinning head through meter and extruded, enter coagulating bath vertically downward and be spun to doughnut, coagulating bath China and foreign countries lime set is 25 DEG C of pure water, interior lime set during film forming to be mass concentration be 15% calcium chloride water, temperature controls at 18 DEG C; The film silk spun out, through rinsing, sizing, namely can be made into membrane module.Record doughnut data as follows: water flux 780L/hm
2, tensile break strength 6.2MPa, elongation at break 92%, interior pressure bubble point pressure 10.4MPa, external pressure pressure at failure 6MPa, the structure of doughnut cross section is shown in accompanying drawing 1.
Comparative example 1
(1) 1-METHYLPYRROLIDONE 72kg is added in stirred tank, again the Corvic 16kg of K value 65 is added in stirred tank, stir, after Corvic is swelling, add the bipolymer copolymerization ratio 72:28 of the bipolymer 4kg(Styrene And Chloroalkyl Acrylates of Styrene And Chloroalkyl Acrylates), be uniformly mixed, Polyvinyl alcohol 8kg in the most backward stirred tank, continues stirring 8 hours, obtained casting solution, in whole process, the temperature of stirred tank controls at 66 DEG C;
(2) by casting solution standing and defoaming 3 hours, the present invention adopts dry-wet process film: the casting solution after deaeration is got to spinning head through meter and extruded, and enter coagulating bath vertically downward and be spun to doughnut, the medium in inside and outside coagulating bath is 25 DEG C of pure water; The film silk spun out, through rinsing, sizing, namely can be made into membrane module.Record doughnut data as follows: water flux 755 L/hm
2, tensile break strength 4.3MPa, elongation at break 57%, interior pressure bubble point pressure 8.3MPa, external pressure pressure at failure 4.5MPa.
Embodiment 2:
(1) dimethyl formamide 85kg is added in stirred tank, add in stirred tank after again the Corvic 6kg of the Corvic 6kg of K value 60 and K value 90 being mixed, stir, after Corvic is swelling, add the bipolymer copolymerization ratio 60:40 of the bipolymer 2kg(Styrene And Chloroalkyl Acrylates of Styrene And Chloroalkyl Acrylates), be uniformly mixed, Polyvinyl alcohol 1kg in the most backward stirred tank, continue stirring 5 hours, obtained casting solution, in whole process, the temperature of stirred tank controls at 40 DEG C;
(2) by casting solution standing and defoaming 2 hours, the present invention adopts dry-wet process film: the casting solution after deaeration is got to spinning head through meter and extruded, enter coagulating bath vertically downward and be spun to doughnut, coagulating bath China and foreign countries lime set is 10 DEG C of pure water, interior lime set during film forming to be mass concentration be 3% calcium chloride water, temperature controls at 12 DEG C; The film silk spun out, through rinsing, sizing, namely can be made into membrane module.Record doughnut data as follows: water flux 910 L/hm
2, tensile break strength 5.9MPa, elongation at break 88%, interior pressure bubble point pressure 10.1MPa, external pressure pressure at failure 5.8MPa.
Embodiment 3:
(1) dimethylacetylamide 70kg adds in stirred tank, add in stirred tank after again the Corvic 3.1kg of the Corvic 13.9kg of K value 65 and K value 85 being mixed, stir, after Corvic is swelling, add the bipolymer copolymerization ratio 90:10 of the bipolymer 6kg(Styrene And Chloroalkyl Acrylates of Styrene And Chloroalkyl Acrylates), be uniformly mixed, Polyvinyl alcohol 7kg in the most backward stirred tank, continue stirring 10 hours, obtained casting solution, in whole process, the temperature of stirred tank controls at 80 DEG C;
(2) by casting solution standing and defoaming 4 hours, the present invention adopts dry-wet process film: the casting solution after deaeration is got to spinning head through meter and extruded, enter coagulating bath vertically downward and be spun to doughnut, coagulating bath China and foreign countries lime set is 50 DEG C of pure water, interior lime set during film forming to be mass concentration be 25% calcium chloride water, temperature controls at 17 DEG C; The film silk spun out, through rinsing, sizing, namely can be made into membrane module.Record doughnut data as follows: water flux 770L/hm
2, tensile break strength 6.7MPa, elongation at break 98%, interior pressure bubble point pressure 11.5MPa, external pressure pressure at failure 7MPa
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (2)
1. a preparation method for high intensity PVC hollow fiber hyperfiltration, is characterized in that: wherein casting solution is made up of following component by weight percentage: Corvic 12 ~ 21%, hydrophilic resin 2 ~ 10%, additive 1 ~ 9%, and surplus is solvent; Described Corvic is that in the Corvic of 60 ~ 90 two kinds combine by K value, in the Corvic of two kinds of K values by weight: the Corvic that K value is low is 50 ~ 90%, and surplus is the Corvic that K value is high;
Described hydrophilic resin is the bipolymer of Styrene And Chloroalkyl Acrylates, and the bipolymer of described Styrene And Chloroalkyl Acrylates is formed by the styrene of 60 ~ 90% and the acroleic acid polymerization of 10 ~ 40% by weight; Described additive is polyvinyl alcohol; Described solvent be dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE one;
Concrete steps are:
(1) solvent is added in stirred tank, add in stirred tank after again the Corvic of two kinds of K values being mixed in proportion, stir, after Corvic is swelling, add hydrophilic resin, be uniformly mixed, doping in the most backward stirred tank, continues stirring 5 ~ 10 hours, obtained casting solution, in whole process, the temperature of stirred tank controls at 40 ~ 80 DEG C;
(2), by casting solution standing and defoaming 2 ~ 4 hours, then casting solution is extruded by spinning head, enter coagulating bath, phase-splitting film forming; Coagulating bath China and foreign countries lime set is 10 ~ 50 DEG C of water, interior lime set during film forming to be mass concentration be 3 ~ 25% calcium chloride water, temperature controls at 12 ~ 18 DEG C.
2. a high intensity PVC hollow fiber hyperfiltration, is characterized in that: prepared by the method for claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110127999.2A CN102784563B (en) | 2011-05-18 | 2011-05-18 | High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110127999.2A CN102784563B (en) | 2011-05-18 | 2011-05-18 | High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102784563A CN102784563A (en) | 2012-11-21 |
| CN102784563B true CN102784563B (en) | 2014-12-24 |
Family
ID=47150262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110127999.2A Expired - Fee Related CN102784563B (en) | 2011-05-18 | 2011-05-18 | High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102784563B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579469B (en) * | 2018-04-28 | 2020-07-31 | 河北优玖环保科技有限公司 | Hollow polyvinyl chloride membrane and preparation method thereof |
| CN108579438A (en) * | 2018-05-16 | 2018-09-28 | 天津工业大学 | A kind of large-flux anti-pollution Pvc Ultrafiltration Membrane and preparation method thereof |
| CN108579437A (en) * | 2018-05-16 | 2018-09-28 | 天津工业大学 | A kind of big flux resistance to compression ultrafiltration membrane and preparation method thereof |
| CN108579470A (en) * | 2018-05-16 | 2018-09-28 | 天津工业大学 | It is a kind of high-throughput to stablize anti-pollution polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN113856485B (en) * | 2021-11-05 | 2024-01-26 | 无锡达魔材料科技有限公司 | Preparation method of hollow fiber nitrogen-rich membrane for gas separation with compact inner edge of membrane wall |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966132A (en) * | 2005-11-15 | 2007-05-23 | 深圳市诚德来实业有限公司 | PVC hollow fiber ultrafiltration membrane preparation method |
| CN101111559A (en) * | 2005-01-27 | 2008-01-23 | 克勒克纳彭塔普拉斯特有限及两合公司 | Moulding mass made from vinyl chloride polymer or polyvinylchloride film produced from said moulding mass and method for production of afilm or film web |
| CN101195083A (en) * | 2007-06-18 | 2008-06-11 | 海南立昇净水科技实业有限公司 | Hydrophilic polyvinyl chloride alloy hollow fiber filtering film and method for producing the same |
-
2011
- 2011-05-18 CN CN201110127999.2A patent/CN102784563B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101111559A (en) * | 2005-01-27 | 2008-01-23 | 克勒克纳彭塔普拉斯特有限及两合公司 | Moulding mass made from vinyl chloride polymer or polyvinylchloride film produced from said moulding mass and method for production of afilm or film web |
| CN1966132A (en) * | 2005-11-15 | 2007-05-23 | 深圳市诚德来实业有限公司 | PVC hollow fiber ultrafiltration membrane preparation method |
| CN101195083A (en) * | 2007-06-18 | 2008-06-11 | 海南立昇净水科技实业有限公司 | Hydrophilic polyvinyl chloride alloy hollow fiber filtering film and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102784563A (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102784563B (en) | High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method | |
| US9095819B2 (en) | Composition for preparation of hollow fiber porous membrane and preparation method using the same | |
| KR101539608B1 (en) | Polyvinylidene fluoride Hollow Fiber Membranes and Preparation Thereof | |
| CN105664740A (en) | Preparation method of nanocellulose composite polysulfone hollow fiber membrane | |
| CN102698614A (en) | Tubular nanofiltration membrane with multi-layer structure and preparation method thereof | |
| CN104906966A (en) | Cellulose acetate/functionalized graphene mixed media hollow fiber positive osmotic membrane | |
| CN103212302A (en) | Method for preparing macromolecule hollow porous fiber membrane by using chemical reaction inductive phase conversion method | |
| CN102824859B (en) | Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method | |
| CN102836644A (en) | Method for synchronously preparing hollow fiber compound nanofiltration membrane through immersion precipitation phase inversion/interface crosslinking | |
| CN102107121A (en) | Method for preparing hollow fiber microporous membrane by thermally-induced phase separation method | |
| US9415348B2 (en) | Method for preparing aromatic polyamide porous hollow fiber membrane | |
| CN101254422B (en) | High intensity PVC hollow fiber hyperfiltration membrane and method of preparing the same | |
| CN104258742B (en) | Preparation method of cheap ultra-filtration membrane for treating oil producing wastewater | |
| CN112337322A (en) | Poly 4-methyl-1-pentene hollow fiber membrane and preparation method thereof | |
| CN106731901A (en) | Polyester fiber weaves the preparation method of tube enhancement type composite hollow fibre forward osmosis membrane | |
| CN101773794A (en) | Three-component five-hole hollow fibrous membrane and preparation method thereof | |
| CN105233703A (en) | Preparation method of high flux cellulose microfiltration membrane | |
| CN1966132A (en) | PVC hollow fiber ultrafiltration membrane preparation method | |
| KR101530432B1 (en) | Polymer composition for preparing acetylated alkyl cellulose membrane and preparation method of acetylated alkyl cellulose membrane using the same | |
| KR20120094362A (en) | Acetylated alkyl cellulose membrane using thermal induced phase separation and preparing method thereof | |
| CN102974232A (en) | Method for producing anti-pollution modified polyvinylidene fluoride hollow fiber membrane | |
| CN103920398B (en) | A kind of hollow-fibre membrane and preparation method thereof | |
| CN102512987B (en) | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane | |
| CN1235669C (en) | Separation membrane made from cellulose and its preparing method | |
| CN107670504A (en) | A kind of method that the organic tubular nanofiltration membrane of solvent resistant is prepared using bidirectional circulating perfusion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141224 Termination date: 20170518 |