CN103191656B - Preparation method of polymer micro-filtration membrane - Google Patents
Preparation method of polymer micro-filtration membrane Download PDFInfo
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- CN103191656B CN103191656B CN201310110835.8A CN201310110835A CN103191656B CN 103191656 B CN103191656 B CN 103191656B CN 201310110835 A CN201310110835 A CN 201310110835A CN 103191656 B CN103191656 B CN 103191656B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 77
- 239000012528 membrane Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000001471 micro-filtration Methods 0.000 title abstract description 12
- -1 poly(phthalazinone ether sulfone ketone Chemical class 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 61
- 239000000376 reactant Substances 0.000 claims description 53
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 23
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 15
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000011541 reaction mixture Substances 0.000 abstract 2
- 239000003999 initiator Substances 0.000 abstract 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 14
- 229940098773 bovine serum albumin Drugs 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000004907 flux Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012749 thinning agent Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparation method of a polymer micro-filtration membrane. The preparation method comprises the following steps of: carrying out polymerization reaction on a sulfonic acid monomer containing double bonds in an organic solvent containing poly(phthalazinone ether sulfone ketone) under the action of an initiator to obtain a first reaction mixture; then heating to generate a crosslinking reaction to obtain a second reaction mixture; and finally carrying out film forming treatment to obtain the polymer micro-filtration membrane, wherein the poly(phthalazinone ether sulfone ketone) containing phthalazinone. According to the preparation method provided by the invention, the aperture size and the hole density of the polymer micro-filtration membrane can be simply and effectively adjusted by changing the proportions of raw material components in the reaction on the basis of pore-forming through interaction among polymer molecule chains; and meanwhile, reagents used in the preparation process are common reagents and are low in cost and easy for implementation of reaction conditions, and a pore-forming method is convenient and fast.
Description
Technical field
The invention belongs to technical field of membrane separation, particularly relate to a kind of preparation method of polymer micro-filter membrane.
Background technology
Polymer micro-filter membrane is one of Application and Development membrane technology the earliest, is also one of most important filter membrane in separation science now.Polymer micro-filter membrane is using the polymer of natural or Prof. Du Yucang as membrane material, its effect mainly allows the large molecule in gas phase or liquid phase and soluble solid (inorganic salts) etc. to pass through, but the materials such as the suspension of more than 0.1 ~ 10 micron, particulate, bacterium and macromolecule colloid can be retained, be widely used at present in the separating and filtering process of the every field such as food, medicine, electronics, environmental protection.
At present, the preparation method of polymer micro-filter membrane mainly contains mechanical stretching method, track etch method and phase separation method.Mechanical stretching method is mainly used in the special polymeric material film forming of properties, and as polyethylene, polypropylene, polytetrafluoroethylene (PTFE) etc., range of application is narrower, and stretcher investment is large, and thickness, the pore-size distribution of prepared polymer micro-filter membrane are also wayward; Track etch method is a kind of method that can regulate and control pore size, form and density, the film prepared by the method often has regular duct and very narrow pore-size distribution, but, prepared polymer micro-filter fenestra is cylindrical capillary tube, not through, porosity is also lower, and needs to use heavy metal or heavy metal ion accelerator in film-forming process, the cost of this preparation method is significantly improved, limits the range of application of the method; Phase separation method nowadays applies wider a kind of film build method, and comprise Thermal inactive, immerse multiple methods such as being separated, this method is simple to operation, but prepared polymer micro-filter also exists pore size, distribute the shortcoming such as wayward.
As Chinese patent CN101396641A discloses a kind of method that composite thermotropic phase separation method prepares polymer micro-filter membrane, it is first under the condition of 110 ~ 150 DEG C, Kynoar and composite thinning agent are dissolved in a kettle. and makes film forming liquid, again above-mentioned film forming liquid, polyethylene glycol and dimethylacetylamide are clamp-oned simultaneously the compound cold quenching liquid of 4 ~ 15 DEG C, there is compound phase separating reaction and generate hollow-fibre membrane base, then under the condition of 5 ~ 80 DEG C, above-mentioned hollow-fibre membrane base is put into extract and extracts composite thinning agent, finally obtain hollow fiber microfiltration membrane.But pore size and the hole density of the microfiltration membranes that said method prepares can not regulate and control.
Summary of the invention
In view of this, the technical problem to be solved in the present invention there are provided a kind of preparation method of polymer micro-filter membrane, and method provided by the invention can prepare pore size and the adjustable polymer micro-filter membrane of hole density.
The invention discloses a kind of preparation method of polymer micro-filter membrane, comprise the following steps:
A) under the effect of initator, the polymerization reaction take place in containing the organic solution of poly (aryl ether sulfone ketone) of the sulfonic acid monomers containing double bond, obtains the first reactant mixture; Described poly (aryl ether sulfone ketone) is the poly (aryl ether sulfone ketone) containing phthalazone;
B) heat up above-mentioned first reactant mixture generation cross-linking reaction, obtains the second reactant mixture;
C) above-mentioned second reactant mixture is carried out film forming process, obtain polymer micro-filter membrane.
Preferably, described initator is azodiisobutyronitrile.
Preferably, in described organic solution, organic solvent is 1-Methyl-2-Pyrrolidone.
Preferably, the described sulfonic acid monomers containing double bond is styrene sulfonic acid class monomer or vinyl sulfonic acid class monomer.
Preferably, described styrene sulfonic acid class monomer is the mixture of styrene sulfonic acid or styrene sulfonic acid and SSS; Described vinyl sulfonic acid class monomer is the mixture of vinyl sulfonic acid or vinyl sulfonic acid and sodium vinyl sulfonate.
Preferably, described styrene sulfonic acid is (0.1 ~ 0.7) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1; Described SSS is (0 ~ 0.5) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1; Described vinyl sulfonic acid is (0.1 ~ 0.7) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1; Described sodium vinyl sulfonate is (0 ~ 0.5) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1.
Preferably, described steps A) be specially:
A1) by the sulfonic acid monomers containing double bond be dissolved in 1-Methyl-2-Pyrrolidone containing the poly (aryl ether sulfone ketone) of phthalazone, pre-polymerization liquid is obtained;
A2) in described pre-polymerization liquid, add initator, polymerization reaction take place under the protection of nitrogen, obtain the first reactant mixture.
Preferably, the mass percent concentration of described pre-polymerization liquid is 15 ~ 25%.
Preferably, the temperature of described polymerisation is 60 ~ 90 DEG C, and the reaction time is 3 ~ 7 hours.
Preferably, the temperature of described cross-linking reaction is 110 ~ 150 DEG C, and the reaction time is 1 ~ 5 hour.
The invention provides a kind of preparation method of polymer micro-filter membrane, by the sulfonic acid monomers containing double bond, containing the poly (aryl ether sulfone ketone) of phthalazone and initator polymerization reaction take place in organic solution, obtain the first reactant mixture, and then the generation cross-linking reaction that heats up obtains the second reactant mixture, finally the second reactant mixture is carried out film forming process, obtain polymer micro-filter membrane.Compared with prior art, the present invention with the sulfonic acid monomers containing double bond, containing the poly (aryl ether sulfone ketone) of phthalazone and initator for the sulfonic acid monomers first polymerization reaction take place of raw material in organic solvent containing double bond, then with the poly (aryl ether sulfone ketone) generation cross-linking reaction containing phthalazone after heating up, in cross-linking reaction process, containing the sulfonic acid group (-SO in the sulfonic acid monomers of double bond
3h) basic group (-N=) and in poly (aryl ether sulfone ketone) in naphthyridine ketone structure is reacted by ionomer and forms acid ion alkali ion pair, enhance the interaction between the polymer of the sulfonic acid monomers containing double bond and poly (aryl ether sulfone ketone) strand, make two kinds of polymer molecular chains close to each other, thus discharge the solvent be present between two kinds of polymer chains, finally carry out film forming process again, solvent droplets is volatilized, and leaves cavity, forms the hole in polymer micro-filter membrane.Formation basic theory due to hole is the interaction based on polymer molecule interchain, therefore just can regulate simply and effectively the pore size of polymer micro-filter membrane and hole density by means of only the proportioning changing reaction Raw component.Meanwhile, the reagent used in preparation process is common agents, and cost is low and reaction condition is easy to realization, and film build method is convenient.Experimental result shows, the present invention is by regulating the proportioning of reaction Raw component, and make the pore size of polymer filtration film there occurs change, under the pressure of 0.01MPa, pure water flux is 25 ~ 61Lm
-2h
-1.
Accompanying drawing explanation
Fig. 1 is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 1;
Fig. 2 is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 2;
Fig. 3 is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 3;
Fig. 4 is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 4;
Fig. 5 is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 5;
Fig. 6 is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 6.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just in order to further illustrate the features and advantages of the present invention, instead of the restriction to invention claim.
The invention provides a kind of preparation method of polymer micro-filter membrane, comprise the following steps:
A) under the effect of initator, the polymerization reaction take place in containing the organic solution of poly (aryl ether sulfone ketone) of the sulfonic acid monomers containing double bond, obtains the first reactant mixture; Described poly (aryl ether sulfone ketone) is the poly (aryl ether sulfone ketone) containing phthalazone;
B) heat up above-mentioned first reactant mixture generation cross-linking reaction, obtains the second reactant mixture;
C) above-mentioned second reactant mixture is carried out film forming process, obtain polymer micro-filter membrane.
The present invention with the sulfonic acid monomers containing double bond, containing the poly (aryl ether sulfone ketone) of phthalazone and initator for raw material polymerization reaction take place in organic solvent, obtain the first reactant mixture, and then the generation cross-linking reaction that heats up obtains the second reactant mixture, finally the second reactant mixture is carried out film forming process, obtain polymer micro-filter membrane.The present invention is by containing the sulfonic acid group (-SO in the sulfonic acid monomers of double bond
3h) basic group (-N=) and in poly (aryl ether sulfone ketone) in naphthyridine ketone structure is reacted by ionomer and forms acid ion alkali ion pair, enhance the interaction between the polymer of the sulfonic acid monomers containing double bond and poly (aryl ether sulfone ketone) strand, make two kinds of polymer molecular chains close to each other, thus discharge the solvent be present between two kinds of polymer chains, finally carry out film forming process again, solvent droplets is volatilized, and leaves cavity, forms the hole in polymer micro-filter membrane.Formation basic theory due to hole is the interaction based on polymer molecule interchain, therefore just can regulate simply and effectively the pore size of polymer micro-filter membrane and hole density by means of only the proportioning changing reaction Raw component.Meanwhile, the reagent used in preparation process is common agents, and cost is low and reaction condition is easy to realization, and film build method is convenient.
The present invention, is not particularly limited its source containing poly (aryl ether sulfone ketone) and the PPESK of phthalazone for raw material with the poly (aryl ether sulfone ketone) containing phthalazone, commercially.
The present invention is with the sulfonic acid monomers containing double bond for raw material, and the described sulfonic acid monomers containing double bond is preferably styrene sulfonic acid class monomer or vinyl sulfonic acid class monomer; Wherein styrene sulfonic acid class monomer can be the mixture of styrene sulfonic acid or styrene sulfonic acid and SSS, and vinyl sulfonic acid class monomer can be the mixture of vinyl sulfonic acid or vinyl sulfonic acid and sodium vinyl sulfonate.
In the present invention, when the described sulfonic acid monomers containing double bond is the mixture of styrene sulfonic acid or styrene sulfonic acid and SSS, styrene sulfonic acid is preferably (0.1 ~ 0.7) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1, be more preferably (0.3 ~ 0.5): 1, SSS is (0 ~ 0.5) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1, is more preferably (0.2 ~ 0.3): 1; When the described sulfonic acid monomers containing double bond is the mixture of vinyl sulfonic acid or vinyl sulfonic acid and sodium vinyl sulfonate, vinyl sulfonic acid is (0.1 ~ 0.7) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1, be more preferably (0.3 ~ 0.5): 1, sodium vinyl sulfonate is (0 ~ 0.5) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1, is more preferably (0.2 ~ 0.3): 1.
The source of sodium p styrene sulfonate of the present invention and sodium vinyl sulfonate is not particularly limited, commercially.The source of p styrene sulfonic acid of the present invention is not particularly limited, and can commercially, also can prepare in accordance with the following methods:
By the aqueous solution of SSS by strong acidic ion exchange column, obtain the aqueous solution of styrene sulfonic acid, by the water of the aqueous solution of above-mentioned styrene sulfonic acid in rotary evaporator removing solution, obtain styrene sulfonic acid;
The concentration of the present invention to the aqueous solution of described SSS is not particularly limited, with concentration range well known to those skilled in the art; Described strong acidic ion exchange column is not particularly limited, with strong acidic ion switching equipment well known to those skilled in the art; Described rotary evaporator is not particularly limited, the rotary evaporation devices known with art technology.
The source of the present invention to vinyl sulfonic acid is not particularly limited, and can commercially, also can prepare in accordance with the following methods:
By the aqueous solution of sodium vinyl sulfonate by strong acidic ion exchange column, obtain the aqueous solution of vinyl sulfonic acid, by the water of the aqueous solution of above-mentioned vinyl sulfonic acid in rotary evaporator removing solution, obtain vinyl sulfonic acid;
The concentration of the present invention to the aqueous solution of described sodium vinyl sulfonate is not particularly limited, with concentration range well known to those skilled in the art; Described strong acidic ion exchange column is not particularly limited, with strong acidic ion switching equipment well known to those skilled in the art; The present invention is not particularly limited described rotary evaporator, the rotary evaporation devices known with art technology.
The present invention is raw materials used, is not particularly limited, commercially buys its source.
The present invention is under the effect of initator, by the polymerization reaction take place in containing the organic solution of poly (aryl ether sulfone ketone) of the sulfonic acid monomers containing double bond, obtain the first reactant mixture, described poly (aryl ether sulfone ketone) is the poly (aryl ether sulfone ketone) containing phthalazone, and this process is preferably:
A1) by the sulfonic acid monomers containing double bond be dissolved in 1-Methyl-2-Pyrrolidone containing the poly (aryl ether sulfone ketone) of phthalazone, pre-polymerization liquid is obtained;
A2) in described pre-polymerization liquid, add initator, polymerization reaction take place under the protection of nitrogen, obtain the first reactant mixture.
First the present invention dissolves in organic solvent by the sulfonic acid monomers containing double bond with containing the poly (aryl ether sulfone ketone) of phthalazone, obtains pre-polymerization liquid.Described organic solvent is preferably 1-Methyl-2-Pyrrolidone, and described pre-polymerization liquid mass percent concentration is preferably 15 ~ 25%, is more preferably 18 ~ 22%.Then in above-mentioned pre-polymerization liquid, add initator, polymerization reaction take place under the protection of nitrogen, obtain the first reactant mixture, described initator is preferably azodiisobutyronitrile; Described initator is preferably (0.01 ~ 0.10) with the ratio of the sulfonic acid monomers containing double bond: 1, is more preferably (0.04 ~ 0.06): 1.Sulfonic acid monomers containing double bond is polymerization reaction take place under the effect of initator, and the temperature of described polymerisation is preferably 60 ~ 90 DEG C, is more preferably 70 ~ 80 DEG C; The described reaction time is preferably 3 ~ 7 hours, is more preferably 4 ~ 6 hours.The present invention preferably carries out polymerisation in the condition stirred; The present invention is not particularly limited the source of nitrogen and purity, with technical requirement well known to those skilled in the art; The method of the present invention to nitrogen protection is not particularly limited, with guard method well known to those skilled in the art; The present invention does not all specially require the container of polymerization reaction take place and mode of heating, with standard operation well known to those skilled in the art.
The present invention, after obtaining the first reactant mixture, continues intensification and makes the first reactant mixture generation cross-linking reaction, obtain the second reactant mixture.Containing the sulfonic acid group (-SO in the sulfonic acid monomers of double bond
3h) basic group (-N=) and in poly (aryl ether sulfone ketone) in naphthyridine ketone structure is reacted by ionomer and forms acid ion alkali ion pair, and for follow-up pore-forming creates conditions, the temperature of described cross-linking reaction is preferably 110 ~ 150 DEG C, is more preferably 125 ~ 135 DEG C; The described reaction time is preferably 1 ~ 5 hour, is more preferably 2 ~ 4 hours; The present invention preferably carries out polymerisation in the condition stirred.
The present invention is carried out film forming process after obtaining the second reactant mixture, obtains polymer micro-filter membrane, and detailed process is preferably carried out according to following steps:
Second reactant mixture is put into airtight container to leave standstill, leave standstill complete the second reactant mixture film forming in the plane by above-mentioned after sloughing bubble, and oven dry obtains polymer micro-filter membrane.Described time of repose is preferably 10 ~ 25 hours, is more preferably 12 ~ 22 hours; Described bake out temperature is preferably 50 ~ 80 DEG C, is more preferably 60 ~ 70 DEG C.The present invention does not specially require airtight container, with closed container well known to those skilled in the art; The present invention does not specially require above-mentioned one-tenth membrane plane, is preferably glass plate or polyfluortetraethylene plate, is more preferably glass plate; The present invention does not specially require drying plant, with baking oven well known to those skilled in the art.
After obtaining polymer micro-filter membrane, it is tested, result shows, the polymer micro-filter membrane prepared under styrene sulfonic acid, SSS and the mol ratio containing the poly (aryl ether sulfone ketone) of phthalazone are the condition of 0.17:0.5:1 is under 0.01MPa pressure, above-mentioned polymer micro-filter membrane is 96% to the rejection of bovine serum albumin, and pure water flux is 43Lm
-2h
-1, after the proportioning by adjustment raw material components, obtaining polymer micro-filter membrane to the rejection of bovine serum albumin is 90 ~ 96%, and pure water flux is 25 ~ 61Lm
-2h
-1.
In order to understand the present invention further, below in conjunction with embodiment, the preparation method to polymer micro-filter membrane provided by the invention is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
15.06g1-N-methyl-2-2-pyrrolidone N-(NMP) is put into there-necked flask, then add wherein 1.0mmol styrene sulfonic acid (SSH), 10.0mmol containing phthalazone poly (aryl ether sulfone ketone) (PPESK) to completely dissolve obtain pre-polymerization liquid.Then in above-mentioned pre-polymerization liquid, 0.011g azodiisobutyronitrile (AIBN) is added; and stir under the protection of nitrogen and heat; polymerisation is carried out under the condition of the permanent gentle agitation of 80 DEG C; the first reactant mixture is obtained after 4 hours; again above-mentioned first reactant mixture heated up and keep other reaction conditions constant; under the condition of constant temperature 120 DEG C, carry out cross-linking reaction, after 2 hours, obtain the second reactant mixture.The reagent bottle above-mentioned second reactant mixture being placed in sealing leaves standstill 10 hours, and slough bubble, finally, natural casting film-forming on the glass plate of smooth pieces also puts into baking oven, dries, obtain polymer micro-filter membrane under the constant temperature of 80 DEG C.
After obtaining polymer micro-filter membrane, test it, result shows, under 0.01MPa pressure, pure water flux is 25Lm
-2h
-1, the rejection of bovine serum albumin (BSA) is 96%.
Carry out sem observation to the cross section of resulting polymers microfiltration membranes, result is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 1 see Fig. 1, Fig. 1.
Embodiment 2
26.18g1-N-methyl-2-2-pyrrolidone N-(NMP) is put into there-necked flask, add 3.0mmol styrene sulfonic acid (SSH), 1.5mmol SSS (SSS) more wherein, 10.5mmol obtains pre-polymerization liquid containing the poly (aryl ether sulfone ketone) (PPESK) of phthalazone to dissolving completely.Then in above-mentioned pre-polymerization liquid, 0.009g azodiisobutyronitrile (AIBN) is added; and stir under the protection of nitrogen and heat; polymerisation is carried out under the condition of the permanent gentle agitation of 70 DEG C; the first reactant mixture is obtained after 5 hours; again above-mentioned first reactant mixture heated up and keep other reaction conditions constant; under the condition of constant temperature 130 DEG C, carry out cross-linking reaction, after 3 hours, obtain the second reactant mixture.The reagent bottle above-mentioned second reactant mixture being placed in sealing leaves standstill 10 hours, and slough bubble, finally, natural casting film-forming on the glass plate of smooth pieces also puts into baking oven, dries, obtain polymer micro-filter membrane under the constant temperature of 80 DEG C.
After obtaining polymer micro-filter membrane, test it, result shows, under 0.01MPa pressure, pure water flux is 53Lm
-2h
-1, the rejection of bovine serum albumin (BSA) is 91%.
Carry out sem observation to the cross section of resulting polymers microfiltration membranes, result is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 2 see Fig. 2, Fig. 2.
Embodiment 3
15.89g1-N-methyl-2-2-pyrrolidone N-(NMP) is put into there-necked flask, add 3.6mmol styrene sulfonic acid (SSH), 1.2mmol SSS (SSS) more wherein, 7.2mmol obtains pre-polymerization liquid containing the poly (aryl ether sulfone ketone) (PPESK) of phthalazone to dissolving completely.Then in above-mentioned pre-polymerization liquid, 0.091g azodiisobutyronitrile (AIBN) is added; and stir under the protection of nitrogen and heat; polymerisation is carried out under the condition of the permanent gentle agitation of 90 DEG C; the first reactant mixture is obtained after 3 hours; again above-mentioned first reactant mixture heated up and keep other reaction conditions constant; under the condition of constant temperature 110 DEG C, carry out cross-linking reaction, after 5 hours, obtain the second reactant mixture.The reagent bottle above-mentioned second reactant mixture being placed in sealing leaves standstill 10 hours, and slough bubble, finally, natural casting film-forming on the glass plate of smooth pieces also puts into baking oven, dries, obtain polymer micro-filter membrane under the constant temperature of 80 DEG C.
After obtaining polymer micro-filter membrane, test it, result shows, under 0.01MPa pressure, pure water flux is 61Lm
-2h
-1, the rejection of bovine serum albumin (BSA) is 90%.
Carry out sem observation to the cross section of resulting polymers microfiltration membranes, result is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 3 see Fig. 3, Fig. 3.
Embodiment 4
12.55g1-N-methyl-2-2-pyrrolidone N-(NMP) is put into there-necked flask, add 1.2mmol styrene sulfonic acid (SSH), 3.6mmol SSS (SSS) more wherein, 7.2mmol obtains pre-polymerization liquid containing the poly (aryl ether sulfone ketone) (PPESK) of phthalazone to dissolving completely.Then in above-mentioned pre-polymerization liquid, 0.029g azodiisobutyronitrile (AIBN) is added; and stir under the protection of nitrogen and heat; polymerisation is carried out under the condition of the permanent gentle agitation of 120 DEG C; the first reactant mixture is obtained after 7 hours; again above-mentioned first reactant mixture heated up and keep other reaction conditions constant; under the condition of constant temperature 140 DEG C, carry out cross-linking reaction, after 4 hours, obtain the second reactant mixture.The reagent bottle above-mentioned second reactant mixture being placed in sealing leaves standstill 10 hours, and slough bubble, finally, natural casting film-forming on the glass plate of smooth pieces also puts into baking oven, dries, obtain polymer micro-filter membrane under the constant temperature of 80 DEG C.
After obtaining polymer micro-filter membrane, test it, result shows, under 0.01MPa pressure, pure water flux is 43Lm
-2h
-1, the rejection of bovine serum albumin (BSA) is 96%.
Carry out sem observation to the cross section of resulting polymers microfiltration membranes, result is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 4 see Fig. 4, Fig. 4.
Embodiment 5
12.49g1-N-methyl-2-2-pyrrolidone N-(NMP) is put into there-necked flask, add 3.6mmol vinyl sulfonic acid (SVH), 1.2mmol sodium vinyl sulfonate (SVS) more wherein, 7.2mmol obtains pre-polymerization liquid containing the poly (aryl ether sulfone ketone) (PPESK) of phthalazone to dissolving completely.Then in above-mentioned pre-polymerization liquid, 0.027g azodiisobutyronitrile (AIBN) is added; and stir under the protection of nitrogen and heat; polymerisation is carried out under the condition of the permanent gentle agitation of 70 DEG C; the first reactant mixture is obtained after 7 hours; again above-mentioned first reactant mixture heated up and keep other reaction conditions constant; under the condition of constant temperature 110 DEG C, carry out cross-linking reaction, after 5 hours, obtain the second reactant mixture.The reagent bottle above-mentioned second reactant mixture being placed in sealing leaves standstill 10 hours, and slough bubble, finally, natural casting film-forming on the glass plate of smooth pieces also puts into baking oven, dries, obtain polymer micro-filter membrane under the constant temperature of 80 DEG C.
After obtaining polymer micro-filter membrane, test it, result shows, under 0.01MPa pressure, pure water flux is 55Lm
-2h
-1, the rejection of bovine serum albumin (BSA) is 92%.
Carry out sem observation to the cross section of resulting polymers microfiltration membranes, result is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 5 see Fig. 5, Fig. 5.
Embodiment 6
9.53g1-N-methyl-2-2-pyrrolidone N-(NMP) is put into there-necked flask, add 1.2mmol vinyl sulfonic acid (SVH), 3.6mmol sodium vinyl sulfonate (SVS) more wherein, 7.2mmol obtains pre-polymerization liquid containing the poly (aryl ether sulfone ketone) (PPESK) of phthalazone to dissolving completely.Then in above-mentioned pre-polymerization liquid, 0.048g azodiisobutyronitrile (AIBN) is added; and stir under the protection of nitrogen and heat; polymerisation is carried out under the condition of the permanent gentle agitation of 80 DEG C; the first reactant mixture is obtained after 3 hours; again above-mentioned first reactant mixture heated up and keep other reaction conditions constant; under the condition of constant temperature 150 DEG C, carry out cross-linking reaction, after 1 hour, obtain the second reactant mixture.The reagent bottle above-mentioned second reactant mixture being placed in sealing leaves standstill 10 hours, and slough bubble, finally, natural casting film-forming on the glass plate of smooth pieces also puts into baking oven, dries, obtain polymer micro-filter membrane under the constant temperature of 80 DEG C.
After obtaining polymer micro-filter membrane, test it, result shows, under 0.01MPa pressure, pure water flux is 37Lm
-2h
-1, the rejection of bovine serum albumin (BSA) is 95%.
Carry out sem observation to the cross section of resulting polymers microfiltration membranes, result is the cross-sectional scanning electron microscope figure of the polymer micro-filter membrane of preparation in the embodiment of the present invention 6 see Fig. 6, Fig. 6.
Above the preparation method of a kind of polymer micro-filter membrane provided by the present invention is described in detail.Apply a concrete example herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (9)
1. a preparation method for polymer micro-filter membrane, comprises the following steps:
A) under the effect of initator, the polymerization reaction take place in containing the organic solution of poly (aryl ether sulfone ketone) of the sulfonic acid monomers containing double bond, obtains the first reactant mixture; Described poly (aryl ether sulfone ketone) is the poly (aryl ether sulfone ketone) containing phthalazone;
The described sulfonic acid monomers containing double bond is styrene sulfonic acid class monomer or vinyl sulfonic acid class monomer;
B) heat up above-mentioned first reactant mixture generation cross-linking reaction, obtains the second reactant mixture;
C) above-mentioned second reactant mixture is carried out film forming process, obtain polymer micro-filter membrane.
2. preparation method according to claim 1, is characterized in that, described initator is azodiisobutyronitrile.
3. preparation method according to claim 1, is characterized in that, in described organic solution, organic solvent is 1-Methyl-2-Pyrrolidone.
4. preparation method according to claim 1, is characterized in that, described styrene sulfonic acid class monomer is the mixture of styrene sulfonic acid or styrene sulfonic acid and SSS; Described vinyl sulfonic acid class monomer is the mixture of vinyl sulfonic acid or vinyl sulfonic acid and sodium vinyl sulfonate.
5. preparation method according to claim 4, is characterized in that, described styrene sulfonic acid is (0.1 ~ 0.7) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1; Described SSS is (0 ~ 0.5) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1; Described vinyl sulfonic acid is (0.1 ~ 0.7) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1; Described sodium vinyl sulfonate is (0 ~ 0.5) with the mol ratio of the poly (aryl ether sulfone ketone) containing phthalazone: 1.
6. preparation method according to claim 1, is characterized in that, described steps A) be specially:
A1) by the sulfonic acid monomers containing double bond be dissolved in 1-Methyl-2-Pyrrolidone containing the poly (aryl ether sulfone ketone) of phthalazone, pre-polymerization liquid is obtained;
A2) in described pre-polymerization liquid, add initator, polymerization reaction take place under the protection of nitrogen, obtain the first reactant mixture.
7. preparation method according to claim 6, is characterized in that, the mass percent concentration of described pre-polymerization liquid is 15 ~ 25%.
8. preparation method according to claim 6, is characterized in that, the temperature of described polymerisation is 60 ~ 90 DEG C, and the reaction time is 3 ~ 7 hours.
9. preparation method according to claim 6, is characterized in that, the temperature of described cross-linking reaction is 110 ~ 150 DEG C, and the reaction time is 1 ~ 5 hour.
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| CN1544135A (en) * | 2003-11-28 | 2004-11-10 | 清华大学 | Dinitrogen phenodiazine polyethersulfone ketone hollow fiber ultra filtration membrane and fabrication method thereof |
| CN101234306A (en) * | 2007-11-13 | 2008-08-06 | 清华大学 | Phthalazine poly(phthalaziane ether sulfone ketone) polymericcompound flat plate ultrafiltration membrane and preparation thereof |
| CN101721926A (en) * | 2009-12-01 | 2010-06-09 | 大连理工大学 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
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| CN1544135A (en) * | 2003-11-28 | 2004-11-10 | 清华大学 | Dinitrogen phenodiazine polyethersulfone ketone hollow fiber ultra filtration membrane and fabrication method thereof |
| CN101234306A (en) * | 2007-11-13 | 2008-08-06 | 清华大学 | Phthalazine poly(phthalaziane ether sulfone ketone) polymericcompound flat plate ultrafiltration membrane and preparation thereof |
| CN101721926A (en) * | 2009-12-01 | 2010-06-09 | 大连理工大学 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
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| 聚醚砜酮合金超滤膜的制备及表征;魏菊等;《膜科学与技术》;20070228;第27卷(第01期);50-54 * |
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