CN104761725A - Symmetric well-defined structure comb-shaped amphiphilic polymer and super hydrophilic modified polymer hollow fiber film - Google Patents
Symmetric well-defined structure comb-shaped amphiphilic polymer and super hydrophilic modified polymer hollow fiber film Download PDFInfo
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Abstract
The present invention discloses a symmetrical well-defined structure comb-shaped amphiphilic polymer and a super hydrophilic modified polymer hollow fiber film. The polymer main chain is polyphosphazene comprising alternate nitrogen and phosphorus atoms, each structural unit of the polyphosphazene main chain is respectively connected with a hydrophobic chain alkyl secondary amine and a hydrophilic chain end amino polyether side group, and the structure is shown as formula (I). The fiber film is a hollow fiber film containing the polymer. The invention also discloses a method for preparing the polymer and the fiber film. By hydrophobic interactions between the amphiphilic polymer side hydrophobic chains and the hydrophobic polymer film material, comb-shaped amphiphilic polyphosphazene is stably attached to the surface of the polymer film hole, and the hydrophilic chain can effectively improve the polymer hollow fiber separation membrane surface hydrophilicity and anti pollution performance, and improves the separation efficiency. The polymer has good biological compatibility and neutral degradation degradability, and is non-toxic.
Description
Technical field
The present invention relates to polymeric film art, be specifically related to the polymeric hollow fibre separatory membrane of a kind of symmetrical ordered structure pectination amphipathic nature polyalcohol and super hydrophilic modifying.
Background technology
Polymer separation film material has been widely used in the fields such as industry, agricultural, medicine, environmental protection, and membrane separation technique has efficient, energy-conservation feature, for save energy, raise the efficiency, environment purification etc. made significant contribution.But separation membrane conventional mostly at present is the macromolecular materials such as polyethylene, polypropylene, polyacrylonitrile, polysulfones, polyethersulfone, polyvinylidene difluoride (PVDF) or tetrafluoroethylene, this kind of surface energy polymer is low, hydrophobicity is stronger, when processing aqueous phase separation system, fluid is high through the mass transfer driving force of polymer separation film, energy consumption is large, and water flux is low; In addition, this kind of hydrophobic membrane materials surface very easily impurity such as adsorb organic compound and protein, produces concentration polarization, film is heavily polluted, thus causes flux sharply to decline, and the further genralrlization that these shortcomings constrain them is applied.
Adopt process for modifying surface can optimize the surface property of separation membrane, especially hydrophilicity, and don't the bulk properties destroying it, can improve the service efficiency of separation membrane, and extend its work-ing life.Up to the present, developed and had multiple different methods to can be used for surface of separating film of polymer hydrophilic modifying, be mainly divided into physical method and chemical process.The former is as physics cladding process, although it is simple, owing to just fixing surface-modifying agent by physisorption, cause surface-modifying agent easily to run off, wetting ability in use declines gradually.The method of chemical modification has a lot, mainly comprises ultraviolet light irradiation graft modification (CN1618509), surface plasma process (CN1539550), γ – x radiation x modification (CN1569934), ozone graft modification (CN1640533) and surfactant-coated modification (CN1257747) etc.Above hydrophilic modification method also exist active particle density not strong, the inconvenient operation of easy-regulating, radiation, be unfavorable for continuous operation, consume energy the shortcoming such as large.
In addition, existing polymer separation film hydrophilic modification method (comprising the methods such as surface chemical modification, surface physics coating and blended amphipathic nature polyalcohol), hydrophilic modifying effect is still also undesirable, hydrophilic modifying caudacoria water contact angle, still more than 40 °, does not reach desirable polymer separation film antipollution effect; Except hydrophilic modifying poor effect, modifying polymer film hydrophilicity often can not steady in a long-termly exist, particularly hydrophilic modifying polymeric film is immersed in water and runs 1 year or clean 1 week through soda acid (pH=1 ~ 12), and modifying polymer film hydrophilicity is lost substantially.Therefore, be necessary that development is a kind of simply efficiently, be suitable for industrialization quantity-produced and there is permanent stability and Superhydrophilic polymer separation film.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of symmetrical ordered structure pectination amphipathic nature polyalcohol and preparation method thereof.
Another object of the present invention is to polymer hollow fiber membrane that a kind of super hydrophilic modifying is provided and preparation method thereof, in this tunica fibrosa, comprise above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol.
Symmetrical ordered structure pectination amphipathic nature polyalcohol provided by the invention can be applicable to prepare hydrophilic modifying polymer separation film, a kind of symmetrical ordered structure pectination amphipathic nature polyalcohol of brand-new design of the present invention improves the wetting ability of polymeric film as additive, the polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, the polymeric hollow fibre separation membrane surface of obtained super hydrophilic modifying, water droplet energy complete wetting is film surface (namely water contact angle can reach 0 °), and there is long-term hydrophilic stability, the polymeric hollow fibre separatory membrane of described super hydrophilic modifying is immersed in water and cleans more than 10 days more than 3 years ' operation or through soda acid (pH=1 ~ 12), the polymeric hollow fibre separation membrane surface water contact angle of super hydrophilic modifying still can remain on less than 40 °.
In order to realize object of the present invention, the present invention adopts following technical scheme:
A kind of symmetrical ordered structure pectination amphipathic nature polyalcohol, the main chain of described polymkeric substance is the poly phosphazene be alternately made up of nitrogen, phosphorus atom, and each modular construction (-P-N-) on described poly phosphazene main chain connects a hydrophobic chain alkyl secondary amine and a hydrophilic chain Amino Terminated polyether(ATPE) side base respectively, described hydrophobic chain alkyl secondary amine side base and the described hydrophilic chain Amino Terminated polyether(ATPE) side base symmetrical both sides being distributed in described poly phosphazene main chain respectively regularly, the structural formula of described symmetrical ordered structure pectination amphipathic nature polyalcohol is as shown in formula I:
Wherein, x:y is the mol ratio of described hydrophilic chain Amino Terminated polyether(ATPE) side base and described hydrophobic chain alkyl secondary amine side base, and the mol ratio of described hydrophobic chain alkyl secondary amine side base and described hydrophilic chain Amino Terminated polyether(ATPE) side base is 0.45:0.55 ~ 0.5:0.5, m, n is the integer of 2 ~ 18, k is the integer of 400 ~ 2000, and the number-average molecular weight of described symmetrical ordered structure pectination amphipathic nature polyalcohol is 2 ~ 500,000, and molecular weight distributing index is 1.6 ~ 3.5.
In above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, the mol ratio of described hydrophobic chain alkyl secondary amine side base and described hydrophilic chain Amino Terminated polyether(ATPE) is 0.45:0.55 ~ 0.5:0.5, i.e. (0.45-0.5): (0.5-0.55), particularly, the mol ratio of the two can be 0.45:0.55,0.46:0.54,0.47:0.52,0.48:0.52,0.5:0.5;
In above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, the general molecular formula forming the water-wet side amino-polyether of hydrophilic chain Amino Terminated polyether(ATPE) side base in above-mentioned amphipathic nature polyalcohol is NH
2(CH
2cH
2o)
knH
2, wherein k is the integer of 400 ~ 2000; Particularly, k can be 400,600,800,1000,1200,1500,1600,1800,2000.
In above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, the general molecular formula forming the hydrophobic alkyl secondary amine of hydrophobic chain alkyl secondary amine side base in above-mentioned amphipathic nature polyalcohol is CH
3(CH
2)
m(NH) (CH
2)
ncH
3, wherein, m, n are the integer of 2 ~ 18, and particularly, m, n can distinguish 2,4,6,8,10,12,14,16,18, m, n can be identical or different; Preferably, the value of m and n is identical, can ensure the symmetrical ordered structure of described amphipathic nature polyalcohol so better.
A preparation method for above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, comprises the steps:
Step one, hexachlorocyclotriphosphazene compound is placed in sealed reaction vessel, under vacuum high-temperature condition, carry out thermal-ring-opening polymerization 12 ~ 72 hours, obtain polydichlorophosphazene elastomerics, the elastomeric general formula of described polydichlorophosphazene is as shown in formula II::
Wherein, i is integer;
Step 2, under protection of inert gas, the obtained polydichlorophosphazene elastomerics of step one and the first organic solvent is added in another reactor, be mixed with the polydichlorophosphazene elastomer solution that concentration is 2 ~ 20wt%, first in described polydichlorophosphazene elastomer solution, drip hydrophobic alkyl secondary amine and organic bases, react under room temperature condition after 2 ~ 24 hours and add water-soluble Amino Terminated polyether(ATPE) again, react 2 ~ 24 hours at ambient temperature again, wherein, described polydichlorophosphazene elastomerics, described water-soluble Amino Terminated polyether(ATPE), the mol ratio of described hydrophobic alkyl secondary amine and described organic bases is 1:1 ~ 2:1 ~ 2:1 ~ 4, afterwards the reaction soln obtained precipitation is contained the symmetrical ordered structure pectination amphipathy polyphosphazene of hydrophobic chain alkyl secondary amine and hydrophilic chain Amino Terminated polyether(ATPE) side base and symmetrical ordered structure pectination amphipathic nature polyalcohol of the present invention to obtain main chain both sides.
In the preparation method of above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, as preferably, the condition of vacuum high-temperature described in step one specifically refers to that vacuum tightness is 20 ~ 2000Pa (such as 25Pa, 100Pa, 150Pa, 250Pa, 340Pa, 500Pa, 800Pa, 1000Pa, 1200Pa, 1600Pa, 1800Pa, 1950Pa), and temperature of reaction is 200 ~ 260 DEG C (such as 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C);
In the preparation method of above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, as preferably, the general molecular formula of the water-soluble Amino Terminated polyether(ATPE) described in step 2 is NH
2(CH
2cH
2o)
knH
2, wherein k is the integer of 400 ~ 2000; Particularly, k can be 400,600,800,1000,1200,1500,1600,1800,2000.This water-soluble Amino Terminated polyether(ATPE) is commercially available prod, the Amino Terminated polyether(ATPE) that such as U.S. Texaco/Huntsman company produces.
In the preparation method of above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, as preferably, the general molecular formula of the secondary amine of hydrophobic alkyl described in step 2 is CH
3(CH
2)
m(NH) (CH
2)
ncH
3, wherein, m, n are the integer of 2 ~ 18, and particularly, m, n can be respectively 2,4,6,8,10,12,14,16,18, m, n can be identical or different; Preferably, the value of m and n is identical, can ensure the symmetrical ordered structure of described amphipathic nature polyalcohol so better.This hydrophobic alkyl secondary amine is commercially available prod, the alkyl secondary amine that such as Sigma-Aldrich company produces.
In the preparation method of above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, as preferably, the elastomeric number-average molecular weight of described polydichlorophosphazene obtained in step one is 0.5-2 ten thousand.
In the preparation method of above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, as preferably, the first organic solvent described in step 2 is tetrahydrofuran (THF).
A kind of polymeric hollow fibre separatory membrane of super hydrophilic modifying, described polymeric hollow fibre separatory membrane comprises fluoropolymer resin and above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, and the polymeric hollow fibre separation membrane surface water contact angle of described super hydrophilic modifying is below 20 °.
In the polymeric hollow fibre separatory membrane of above-mentioned super hydrophilic modifying, as preferably, the mass ratio of described fluoropolymer resin and described symmetrical ordered structure pectination amphipathic nature polyalcohol is 5:1 ~ 1:1, and more preferably, the polymeric hollow fibre separation membrane surface water contact angle of described super hydrophilic modifying is 0 °.
In the polymeric hollow fibre separatory membrane of above-mentioned super hydrophilic modifying, as preferably, described fluoropolymer resin can be any one in polysulfones, polyethersulfone, polyvinylidene difluoride (PVDF), polyacrylonitrile, polyvinyl chloride.
A preparation method for the polymeric hollow fibre separatory membrane of above-mentioned super hydrophilic modifying, comprises the steps:
The preparation process of preparation liquid, fluoropolymer resin, above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, film for additive and the second organic solvent are mixed, under 10 ~ 90 DEG C (such as 15 DEG C, 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C), is uniformly mixed dissolving; After solute dissolves completely, filter cleaner, obtains polymer resin solution, obtains preparation liquid after then using rare gas element deaeration 6 ~ 48h (such as 10h, 15h, 20h, 25h, 35h, 45h);
Masking step, extrudes immersion precipitation liquid by the described preparation liquid obtained from spinning nozzle, and form nascent fibre, after abundant rinsing, taking-up is dried, thus the polymeric hollow fibre separatory membrane of obtained described super hydrophilic modifying.
In the preparation method of the polymeric hollow fibre separatory membrane of above-mentioned super hydrophilic modifying, as preferably, described fluoropolymer resin can be any one in polysulfones, polyethersulfone, polyvinylidene difluoride (PVDF), polyacrylonitrile, polyvinyl chloride.
In the preparation method of the polymeric hollow fibre separatory membrane of above-mentioned super hydrophilic modifying, as preferably, described film for additive be selected from PEG400, PEG600, PEG800, PEG1000, PEG2000, PVP-K17, PVP-K30, PVP-K90 any one or multiple arbitrarily.
In the preparation method of the polymeric hollow fibre separatory membrane of above-mentioned super hydrophilic modifying, as preferably, the second described organic solvent is selected from dimethyl formamide, N,N-dimethylacetamide or N-Methyl pyrrolidone.
In the preparation method of the polymeric hollow fibre separatory membrane of above-mentioned super hydrophilic modifying, as preferably, in the preparation process of described preparation liquid, described fluoropolymer resin in the preparation liquid obtained, described symmetrical ordered structure pectination amphipathic nature polyalcohol, the proportioning of described film for additive and described second organic solvent is: the massfraction of described fluoropolymer resin is 15 ~ 25%, the massfraction of described symmetrical ordered structure pectination amphipathic nature polyalcohol is 5 ~ 15%, the massfraction of described film for additive is 1 ~ 20%, the massfraction of described second organic solvent is 50 ~ 70%.
In the preparation method of the polymeric hollow fibre separatory membrane of above-mentioned super hydrophilic modifying, as preferably, in described masking step, it is obtained after water mixes with described second organic solvent by described coagulant liquid, described in described coagulant liquid, the mass concentration of the second organic solvent is 0-50% (such as 0%, 10%, 20%, 30%, 40%, 48%), that is, coagulant liquid can be replaced with water.
In the present invention, the poly phosphazene macromolecular material that described symmetrical ordered structure pectination amphipathic nature polyalcohol is alternately made up of nitrogen, phosphorus atom with main chain, and the side base on each backbone units structure (-P-N-) of poly phosphazene connects a hydrophobic chain alkyl secondary amine and a hydrophilic chain Amino Terminated polyether(ATPE) respectively, hydrophobic chain and the hydrophilic chain symmetrical both sides being distributed in poly phosphazene main chain respectively on the base of side regularly, and the hydrophobic chain alkyl secondary amine on the base of side and hydrophilic chain Amino Terminated polyether(ATPE) mol ratio are approximately 1:1, and concrete molar ratio range is 0.45:0.55 ~ 0.5:0.5.Described symmetrical ordered structure pectination amphipathic nature polyalcohol is for the preparation of the principle of the polymeric hollow fibre separatory membrane of super hydrophilic modifying: this symmetrical ordered structure pectination amphipathic nature polyalcohol form hydrophobic cluster and can strengthen multiple hydrophobic interaction between polymeric film bulk material further, the larger pectination body structure of amphipathic nature polyalcohol, this symmetrical ordered structure pectination amphipathic nature polyalcohol is not easily run off in the polymeric hollow fibre separatory membrane of super hydrophilic modifying, improves the permanent stability of hydrophilic modifying; The a large amount of enrichment of hollow fiber separation membrane surface in the polymer of symmetrical ordered structure pectination amphipathic nature polyalcohol larger pectinate body water-wet side amino-polyether chain, forms hydrophilic cluster, thus greatly improves the wetting ability on film surface.In addition, because poly phosphazene is a kind of biocompatible materials of excellence, the biological antifouling property of described polymeric hollow fibre separation membrane surface can effectively be improved.Therefore, the hydrophobic chain of the side base of described symmetrical ordered structure pectination amphipathic nature polyalcohol can and hydrophobic polymer mould material between hydrophobic interaction, pectination amphipathic nature polyalcohol is made stably to be attached to polymeric hollow fibre separatory membrane hole surface, hydrophilic chain on amphipathic nature polyalcohol side chain effectively can improve wetting ability and the antifouling property of polymeric hollow fibre separation membrane surface, improves separation efficiency; Greatly improve the stability of amphipathy polyphosphazene in polymeric film material; Polymkeric substance of the present invention has good biocompatibility, and nontoxic, neutral degradation property, has wide application prospect in the field such as biological medicine and protein separation.
The polymeric hollow fibre separatory membrane of described super hydrophilic modifying has excellent wetting ability and antifouling property, the polymeric hollow fibre separation membrane surface water contact angle of described super hydrophilic modifying is below 20 °, and preferably the polymeric hollow fibre separation membrane surface water contact angle of super hydrophilic modifying is 0 °; The polymeric hollow fibre separatory membrane aperture of described super hydrophilic modifying is preferably 0.01 ~ 0.5 μm.
The present invention adopts with symmetrical ordered structure pectination amphipathic nature polyalcohol as masking additive, by with film fluoropolymer resin blending method, utilize symmetrical ordered structure pectination amphipathic nature polyalcohol can in the enrichment of polymeric film hole surface, effective wetting ability and antifouling property improving surface of separating film of polymer, and add film for additive, utilize immersion precipitation phase inversion process spinning, be prepared into the super hydrophilic polymer hollow fiber separating film of symmetrical ordered structure pectination amphipathic nature polyalcohol modification.Its method preparation process is simple, and product hydrophilicity long-term stability can repeatedly use, and good biocompatibility, be conducive to improving the antifouling property such as protein, colloid.
Compared with prior art, beneficial effect of the present invention is:
(1) symmetrical ordered structure pectination amphipathic nature polyalcohol, side base on its poly phosphazene each backbone units structure (-P-N-) connects a hydrophobic chain alkyl secondary amine and a hydrophilic amido polyethers respectively, hydrophobic chain and the hydrophilic chain symmetrical both sides being distributed in poly phosphazene main chain respectively on the base of side regularly, and hydrophobic chain alkyl secondary amine on the base of side and hydrophilic chain Amino Terminated polyether(ATPE) mol ratio are approximately 1:1; Symmetrical ordered structure pectination amphipathic nature polyalcohol easily forms hydrophobic chain cluster and hydrophilic chain cluster;
(2) symmetrical ordered structure pectination amphipathic nature polyalcohol larger pectinate body hydrophilic polyether chain is in a large amount of enrichment in film surface, form hydrophilic cluster, thus greatly improve the wetting ability on film surface, water droplet energy complete wetting is on film surface, and the surface of separating film of polymer water contact angle of prepared super hydrophilic modifying can reach 0 °;
(3) symmetrical ordered structure pectination amphipathic nature polyalcohol similar used is in polymer brush, this symmetrical ordered structure with the larger pectination bodily form easily forms hydrophobic chain cluster, the multiple hydrophobic interaction between polymeric film bulk material can be strengthened further, this kind of symmetrical ordered structure pectination amphipathic nature polyalcohol is not easily run off in polymer separation film, improve the permanent stability of hydrophilic modifying, the polymer separation film of super hydrophilic modifying is immersed in water and cleans more than 10 days more than 3 years ' operation or through soda acid (pH=1 ~ 12), the surface of separating film of polymer water contact angle of super hydrophilic modifying still can remain on less than 40 °.
(4) poly phosphazene has better biocompatibility, non-toxic degradation, and this kind of symmetrical ordered structure pectination amphipathic nature polyalcohol can give biocompatibility and the stable against biological contamination performance of polymer separation film excellence;
(5) prepare solution by the method for physical blending, working condition gentleness, technique are simple, spray silk jet stability good in spinning process, and tunica fibrosa morphological structure can pass easily through and regulate the condition of spinning process to control, and is suitable for suitability for industrialized production.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 20Pa vacuum 200 DEG C of conditions, carry out thermal-ring-opening polymerization 24 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 6500;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is the polydichlorophosphazene solution of 10wt%, first in polydichlorophosphazene elastomer solution, drips N, N-dipropylamine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=2) and triethylamine, react under room temperature condition after 8 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=400), react 8 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-dipropylamine and triethylamine is 1:1:1:2, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.50:0.50 (x:y=0.50:0.50) (being shown below), and its number-average molecular weight is 300,000, and molecular weight distribution is 2.0.
wherein m=n=2; X:y=0.50:0.50.
(3) in the ratio (mass ratio) of 15:5:20:60, dried polysulfones (number-average molecular weight=90000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PEG 400, dimethyl formamide are slowly added in there-necked flask successively, stirring and dissolving is carried out at 60 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 12h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing dimethyl formamide concentration is in the coagulant liquid of 10wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h more successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is less than 20 °, within 10 days, processing caudacoria surface water contact angle at the NaOH aqueous solution successive soaking of pH=12 is 32 °, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are 33 °, are 40 ° after 10 days.
Comparative example 1
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 20Pa vacuum 200 DEG C of conditions, carry out thermal-ring-opening polymerization 24 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 6500;
(2) under nitrogen protection; add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor; compound concentration is the polydichlorophosphazene solution of 10wt%; first in this polydichlorophosphazene solution, drip Tri N-Propyl Amine and triethylamine, react under room temperature condition after 8 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=400), then react 8 hours at ambient temperature, wherein, the mol ratio of polydichlorophosphazene, Amino Terminated polyether(ATPE), Tri N-Propyl Amine and triethylamine is 1:1:1:2, the reaction soln obtained is poured into precipitation in sherwood oil and obtains random amphipathic nature polyalcohol.By to product elemental analysis, the ratio of hydrophobe component is 0.50:0.50 (x:y=0.50:0.50), and its number-average molecular weight is 300,000, and molecular weight distribution is 2.5.
(3) in the ratio (mass ratio) of 15:5:20:60, dried polysulfones (number-average molecular weight=90000), above-mentioned random amphipathic nature polyalcohol, additive PEG 400, dimethyl formamide are slowly added in there-necked flask successively, stirring and dissolving is carried out at 60 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 12h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing dimethyl formamide concentration is in the coagulant liquid of 10wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h more successively, taking-up is dried, the i.e. obtained polymer-modified hollow-fibre membrane of random amphipathic nature polyalcohol, film surface water contact angle is 70 °, within 10 days, processing caudacoria surface water contact angle at the NaOH aqueous solution successive soaking of pH=12 is 78 °, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are 85 °, are 95 ° after 10 days.
Embodiment 2
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 200Pa vacuum 200 DEG C of conditions, carry out thermal-ring-opening polymerization 12 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 5000;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is 20wt% polydichlorophosphazene solution, first in this polydichlorophosphazene solution, drips N, N-dibutylamine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=3) and triethylamine, react under room temperature condition after 12 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=800), react 12 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-dibutylamine and triethylamine is: 1:1.5:1:2, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.54:0.46 (x:y=0.54:0.46).(being shown below), its number-average molecular weight is 20,000, and molecular weight distribution is 3.0.
wherein m=n=3; X:y=0.54:0.46.
(3) in the ratio (mass ratio) of 17:10:15:58 by dried polysulfones (number-average molecular weight=90000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PEG 600, N, N-N,N-DIMETHYLACETAMIDE slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 24h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immerse N, N-N,N-DIMETHYLACETAMIDE concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h more successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is less than 10 °, within 10 days, processing caudacoria surface water contact angle at the NaOH aqueous solution successive soaking of pH=12 is 28 °, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are 30 °, after 10 days be 35 °.
Comparative example 2
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 200Pa vacuum 200 DEG C of conditions, carry out thermal-ring-opening polymerization 12 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 5000;
(2) under nitrogen protection; add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor; compound concentration is 20wt% polydichlorophosphazene solution; first in this polydichlorophosphazene solution, drip n-Butyl Amine 99 and triethylamine, react under room temperature condition after 12 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=800), more at ambient temperature react 12 hours, wherein, the mol ratio of polydichlorophosphazene, Amino Terminated polyether(ATPE), n-Butyl Amine 99 and triethylamine is: 1:1.5:1:3, will obtain reaction soln pour in sherwood oil precipitate obtain random amphipathic nature polyalcohol.By to product elemental analysis, the hydrophobe ratio of random amphipathic nature polyalcohol is 0.54:0.46 (x:y=0.54:0.46), and its number-average molecular weight is 20,000, and molecular weight distribution is 3.5.
(3) in the ratio (mass ratio) of 17:10:15:58 by dried polysulfones (number-average molecular weight=90000), above-mentioned random amphipathic nature polyalcohol, additive PEG 600, N, N-N,N-DIMETHYLACETAMIDE slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 24h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immerse N, N-N,N-DIMETHYLACETAMIDE concentration is in the coagulant liquid of 20%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. obtained polymer-modified hollow-fibre membrane of random amphipathic nature polyalcohol, film surface water contact angle is 65 °, within 10 days, processing caudacoria surface water contact angle at the NaOH aqueous solution successive soaking of pH=12 is 78 °, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are 75 °, are 88 ° after 10 days.
Embodiment 3
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 20Pa vacuum 206 DEG C of conditions, carry out thermal-ring-opening polymerization 72 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 20,000;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is the polydichlorophosphazene solution of 2wt%, first in this polydichlorophosphazene solution, drips N, N-diamyl amine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=4) and triethylamine, react under room temperature condition after 24 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=2000), react 24 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-diamyl amine and triethylamine is: 1:1.5:1.5:3, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.53:0.47 (x:y=0.53:0.47).(being shown below), its number-average molecular weight is 500,000, and molecular weight distribution is 2.8.
wherein m=n=4; X:y=0.53:0.47.
(3) in the ratio (mass ratio) of 15:15:15:55, dried polysulfones (number-average molecular weight=90000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PEG 1000, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 70 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 48h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is 0 °, 20 ° are less than at NaOH aqueous solution successive soaking 10 days process caudacoria surface water contact angle of pH=12, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are less than 20 °, are 30 ° after 10 days.
Comparative example 3
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 200Pa vacuum 200 DEG C of conditions, carry out thermal-ring-opening polymerization 12 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 5000;
(2) under nitrogen protection; add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor; compound concentration is the polydichlorophosphazene solution of 20wt%; first in this polydichlorophosphazene solution, drip n-amylamine and triethylamine, react under room temperature condition after 12 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=2000), react 12 hours at ambient temperature again, wherein, the mol ratio of polydichlorophosphazene, Amino Terminated polyether(ATPE), n-amylamine and triethylamine is: 1:1.5:1:3, the reaction soln obtained is poured into precipitation in sherwood oil and obtains random amphipathic nature polyalcohol.By to product elemental analysis, the hydrophobe ratio of the random amphipathic nature polyalcohol of gained is 0.53:0.47 (x:y=0.53:0.47), and its number-average molecular weight is 20,000, and molecular weight distribution is 2.3.
(3) in the ratio (mass ratio) of 17:10:15:58 by dried polysulfones (number-average molecular weight=90000), above-mentioned random amphipathic nature polyalcohol, additive PEG 600, N, N-N,N-DIMETHYLACETAMIDE slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 24h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immerse N, N-N,N-DIMETHYLACETAMIDE concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. obtained polymer-modified hollow-fibre membrane of random amphipathic nature polyalcohol, film surface water contact angle is 78 °, within 10 days, processing caudacoria surface water contact angle at the NaOH aqueous solution successive soaking of pH=12 is 80 °, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are 85 °, are 90 ° after 10 days.
Embodiment 4
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 500Pa vacuum 250 DEG C of conditions, carry out thermal-ring-opening polymerization 48 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 1.3 ten thousand;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is the polydichlorophosphazene solution of 12wt%, first in this polydichlorophosphazene solution, drips N, N-bis-(dodecyl) amine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=11) and triethylamine, react under room temperature condition after 24 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=2000), react 24 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-bis-(dodecyl) amine and triethylamine is: 1:2:2:4, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.55:0.45 (x:y=0.55:0.45).(being shown below), its number-average molecular weight is 260,000, and molecular weight distribution is 3.2.
wherein m=n=11; X:y=0.45:0.55.
(3) in the ratio (mass ratio) of 18:12:15:55, dried polyethersulfone (number-average molecular weight=100000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PEG 2000, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 24h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is less than 10 °, 30 ° are less than at NaOH aqueous solution successive soaking 10 days process caudacoria surface water contact angle of pH=12, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are less than 30 °, are 35 ° after 10 days.
Embodiment 5
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 1000Pa vacuum 250 DEG C of conditions, carry out thermal-ring-opening polymerization 60 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 1.7 ten thousand;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is the polydichlorophosphazene solution of 8wt%, first in this polydichlorophosphazene solution, drips N, N-bis-(octadecyl) amine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=17) and triethylamine, react under room temperature condition after 24 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=2000), react 24 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-bis-(octadecyl) amine and triethylamine is: 1:2:1:2, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.52:0.48 (x:y=0.52:0.48).(being shown below), its number-average molecular weight is 350,000, and molecular weight distribution is 2.1.
wherein m=n=17; X:y=0.52:0.48.
(3) in the ratio (mass ratio) of 16:15:15:54, dried polyethersulfone (number-average molecular weight=100000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PVP-K17, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 70 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 24h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is for being less than 20 °, 30 ° are less than at NaOH aqueous solution successive soaking 10 days process caudacoria surface water contact angle of pH=12, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are less than 30 °, after 10 days be 38 °.
Embodiment 6
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 2000Pa vacuum 230 DEG C of conditions, carry out thermal-ring-opening polymerization 60 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 1.7 ten thousand;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is the polydichlorophosphazene solution of 8wt%, first in this polydichlorophosphazene solution, drips N, N-bis-(dodecyl) amine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=11) and triethylamine, react under room temperature condition after 24 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=1800), react 24 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-bis-(dodecyl) amine and triethylamine is: 1:1.5:1:3, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.55:0.45 (x:y=0.55:0.45).(being shown below), its number-average molecular weight is 320,000, and molecular weight distribution is 2.2.
wherein m=n=11; X:y=0.55:0.45.
(3) in the ratio (mass ratio) of 20:10:10:60, dried polyethersulfone (number-average molecular weight=100000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PVP-K30, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 70 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 10h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is for being less than 20 °, within 10 days, processing caudacoria surface water contact angle at the NaOH aqueous solution successive soaking of pH=12 is 30 °, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are 35 °, are 40 ° after 10 days.
Embodiment 7
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 100Pa vacuum 250 DEG C of conditions, carry out thermal-ring-opening polymerization 48 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 1.3 ten thousand;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is the polydichlorophosphazene solution of 15wt%, first in this polydichlorophosphazene solution, drips N, N-bis-(dodecyl) amine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=11) and triethylamine, react under room temperature condition after 20 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=2000), react 20 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-bis-(dodecyl) amine and triethylamine is: 1:1:2:4, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.54:0.46 (x:y=0.54:0.46).(being shown below), its number-average molecular weight is 180,000, and molecular weight distribution is 2.5.
wherein m=n=11; X:y=0.54:0.46.
(3) in the ratio (mass ratio) of 20:15:1:64, dried polyvinylidene difluoride (PVDF) (number-average molecular weight=500000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PVP-K90, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 90 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 24h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is for being less than 20 °, within 10 days, processing caudacoria surface water contact angle at the NaOH aqueous solution successive soaking of pH=12 is 33 °, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are 35 °, are 40 ° after 10 days.
Embodiment 8
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 500Pa vacuum 250 DEG C of conditions, carry out thermal-ring-opening polymerization 36 hours, obtain polydichlorophosphazene elastomerics, its number average molecular weight is 9000;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is 20wt% polydichlorophosphazene solution, first in this polydichlorophosphazene solution, drips N, N-bis-(dodecyl) amine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=11) and triethylamine, react under room temperature condition after 24 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=1500), react 24 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-bis-(dodecyl) amine and triethylamine is: 1:2:1:1.5, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.53:0.47 (x:y=0.53:0.47).(being shown below), its number-average molecular weight is 160,000, and molecular weight distribution is 2.6.
wherein m=n=11; X:y=0.53:0.47.
(3) in the ratio (mass ratio) of 18:15:10:57, dried polyvinylidene difluoride (PVDF) (number-average molecular weight=500000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PVP-K30, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 10h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is 0 °, 20 ° are less than at NaOH aqueous solution successive soaking 10 days process caudacoria surface water contact angle of pH=12, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are less than 20 °, are 35 ° after 10 days.
Embodiment 9
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 500Pa vacuum 250 DEG C of conditions, carry out thermal-ring-opening polymerization 36 hours, obtain polydichlorophosphazene elastomerics, its number average molecular weight is 9000;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is 20wt% polydichlorophosphazene solution, first in this polydichlorophosphazene solution, drips N, N-bis-(dodecyl) amine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=11) triethylamine, reacts under room temperature condition after 24 hours and adds Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=1600), react 24 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-bis-(dodecyl) amine and triethylamine is: 1:2:1:3, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.52:0.48 (x:y=0.52:0.48).(being shown below), its number-average molecular weight is 160,000, and molecular weight distribution is 2.9.
wherein m=n=11; X:y=0.52:0.48.
(3) in the ratio (mass ratio) of 25:15:5:55, dried polyacrylonitrile (number-average molecular weight=100000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PVP-K30, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 10h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is less than 20 °, within 10 days, processing caudacoria surface water contact angle at the NaOH aqueous solution successive soaking of pH=12 is 30 °, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are 35 °, are 40 ° after 10 days.
Embodiment 10
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 100Pa vacuum 250 DEG C of conditions, carry out thermal-ring-opening polymerization 48 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 1.3 ten thousand;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is 15wt% polydichlorophosphazene solution, first in this polydichlorophosphazene solution, drips N, N-bis-(dodecyl) amine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=11) and triethylamine, react under room temperature condition after 20 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=2000), react 20 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-bis-(dodecyl) amine and triethylamine is: 1:1.5:1:4, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.55:0.45 (x:y=0.55:0.45).(being shown below), its number-average molecular weight is 180,000, and molecular weight distribution is 1.8.
wherein m=n=11; X:y=0.55:0.45.
(3) in the ratio (mass ratio) of 20:15:1:64, dried polyacrylonitrile (number-average molecular weight=100000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PVP-K90, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 90 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 24h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 10wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, the contact of film surface water is 0 °, 20 ° are less than at NaOH aqueous solution successive soaking 10 days process caudacoria surface water contact angle of pH=12, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are less than 20 °, are 35 ° after 10 days.
Embodiment 11
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 200Pa vacuum 200 DEG C of conditions, carry out thermal-ring-opening polymerization 12 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 5000;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is 20wt% polydichlorophosphazene solution, first in this polydichlorophosphazene solution, drips N, N-dibutylamine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=3) and triethylamine, react under room temperature condition after 12 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=800), react 12 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-dibutylamine and triethylamine is: 1:1.5:1:2,, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.55:0.45 (x:y=0.55:0.45) (being shown below), and its number-average molecular weight is 20,000, and molecular weight distribution is 1.9.
wherein m=n=3; X:y=0.56:0.44.
(3) in the ratio (mass ratio) of 25:10:10:55 by dried polyvinyl chloride (number-average molecular weight=50000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PEG 600, N, N-N,N-DIMETHYLACETAMIDE slowly adds in there-necked flask successively, stirring and dissolving is carried out at 80 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 24h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immerse N, N-N,N-DIMETHYLACETAMIDE concentration is in the coagulant liquid of 20wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is less than 10 °, 20 ° are less than at NaOH aqueous solution successive soaking 10 days process caudacoria surface water contact angle of pH=12, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are less than 20 °, 30 ° are less than after 10 days.
Embodiment 12
(1) hexachlorocyclotriphosphazene is placed in sealed reaction vessel, under 20Pa vacuum 206 DEG C of conditions, carry out thermal-ring-opening polymerization 72 hours, obtain polydichlorophosphazene elastomerics, its number-average molecular weight is 20,000;
(2) under nitrogen protection, add obtained polydichlorophosphazene and tetrahydrofuran solvent in the reactor, compound concentration is 2wt% polydichlorophosphazene solution, first in this polydichlorophosphazene solution, drips N, N-diamylamine CH
3(CH
2)
m(NH) (CH
2)
ncH
3(m, n=4) and triethylamine, react under room temperature condition after 24 hours and add Amino Terminated polyether(ATPE) NH again
2(CH
2cH
2o)
knH
2(k=2000), react 24 hours at ambient temperature again, wherein, polydichlorophosphazene, Amino Terminated polyether(ATPE), N, the mol ratio of N-diamylamine and triethylamine is: 1:1.5:1.5:2, the reaction soln obtained is poured in sherwood oil into the symmetrical ordered structure pectination amphipathic nature polyalcohol precipitating and obtain side base and contain hydrophobic alkyl chain and hydrophilic polyether chain.By to product elemental analysis, the hydrophobe ratio of gained symmetrical ordered structure pectination amphipathic nature polyalcohol is 0.50:0.50 (x:y=0.50:0.50) (being shown below), and its number-average molecular weight is 500,000, and molecular weight distribution is 1.6.
wherein m=n=4; X:y=0.50:0.50.
(3) in the ratio (mass ratio) of 15:15:15:55, dried polyvinyl chloride (number-average molecular weight=50000), above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, additive PEG 1000, N-Methyl pyrrolidone are slowly added in there-necked flask successively, stirring and dissolving is carried out at 70 DEG C, after solute dissolves completely, namely filter cleaner, then obtain preparation liquid with after nitrogen deaeration 48h.
(4) preparation liquid is extruded from spinning nozzle under 2MPa, immersing N-Methyl pyrrolidone concentration is in the coagulant liquid of 30wt%, form nascent fibre, to immerse respectively in deionized water and ultrapure water after rinsing 24h successively, taking-up is dried, the i.e. polymeric hollow fibre separatory membrane of obtained super hydrophilic modifying, film surface water contact angle is less than 20 °, 30 ° are less than at NaOH aqueous solution successive soaking 10 days process caudacoria surface water contact angle of pH=12, the NaClO aqueous solution successive soaking 5 days caudacoria surface water contact angle being 2000ppm in concentration are less than 30 °, are 40 ° after 10 days.
Above-described embodiment is only not used in for illustration of the present invention and limits the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
The surface water contact angle of the tunica fibrosa that table 1 embodiment 1-12 obtains
From the embodiment of upper table 1 and the data of comparative example, the symmetrical ordered structure pectination amphipathic nature polyalcohol of embodiment gained is better than the random amphipathic nature polyalcohol of comparative example's gained for the hydrophilic modifying effect of hollow-fibre membrane.The random amphipathic nature polyalcohol modified hollow fibre membrane of comparative example 1,2 and 3 gained, dry state film water contact angle is more than 65 °, and all symmetrical ordered structure pectination amphipathic nature polyalcohol modification prepared by embodiment of the present invention surpasses hydrophilic hollow fiber film, dry state film water contact angle is less than 20 °, namely has super hydrophilicity.
The random amphipathic nature polyalcohol modified hollow fibre membrane of comparative example 1,2 and 3 gained, after the NaOH aqueous solution successive soaking process in 10 days of pH=12, film surface water contact angle all rises to more than 75 °, and all symmetrical ordered structure pectination amphipathic nature polyalcohol modification prepared by embodiment of the present invention surpasses hydrophilic hollow fiber film, after the NaOH aqueous solution successive soaking process in 10 days of pH=12, film surface water contact angle is all less than 33 °, namely has alkaline-resisting stable persistence super hydrophilicity.
The random amphipathic nature polyalcohol modified hollow fibre membrane of comparative example 1,2 and 3 gained, be that the NaClO aqueous solution successive soaking of 2000ppm is after 10 days through concentration, film surface water contact angle all rises to more than 80 °, and all symmetrical ordered structure pectination amphipathic nature polyalcohol modification prepared by embodiment of the present invention surpasses hydrophilic hollow fiber film, be that the NaClO aqueous solution successive soaking of 2000ppm is after 10 days through concentration, film surface water contact angle is all less than 40 °, namely has sludge proof and stablizes persistence super hydrophilicity.
Claims (10)
1. a symmetrical ordered structure pectination amphipathic nature polyalcohol, it is characterized in that, the main chain of described polymkeric substance is the poly phosphazene be alternately made up of nitrogen, phosphorus atom, and each modular construction (-P-N-) on described poly phosphazene main chain connects a hydrophobic chain alkyl secondary amine and a hydrophilic chain Amino Terminated polyether(ATPE) side base respectively, described hydrophobic chain alkyl secondary amine side base and the described hydrophilic chain Amino Terminated polyether(ATPE) side base symmetrical both sides being distributed in described poly phosphazene main chain respectively regularly, the structural formula of described symmetrical ordered structure pectination amphipathic nature polyalcohol is as shown in formula I:
Wherein, x:y is the mol ratio of described hydrophilic chain Amino Terminated polyether(ATPE) side base and described hydrophobic chain alkyl secondary amine side base, and the mol ratio of described hydrophobic chain alkyl secondary amine side base and described hydrophilic chain Amino Terminated polyether(ATPE) side base is 0.45:0.55 ~ 0.5:0.5, m, n is the integer of 2 ~ 18, k is the integer of 400 ~ 2000, and the number-average molecular weight of described symmetrical ordered structure pectination amphipathic nature polyalcohol is 2 ~ 500,000, and molecular weight distributing index is 1.6 ~ 3.5.
2. symmetrical ordered structure pectination amphipathic nature polyalcohol according to claim 1, is characterized in that, the mol ratio of described hydrophobic chain alkyl secondary amine side base and described hydrophilic chain Amino Terminated polyether(ATPE) is 0.45:0.55 ~ 0.5:0.5.
3. symmetrical ordered structure pectination amphipathic nature polyalcohol according to claim 1, it is characterized in that, the value of described m and n is identical.
4. a preparation method for the arbitrary described symmetrical ordered structure pectination amphipathic nature polyalcohol of claim 1-3, is characterized in that, comprise the steps:
Step one, hexachlorocyclotriphosphazene compound is placed in sealed reaction vessel, under vacuum high-temperature condition, carry out thermal-ring-opening polymerization 12 ~ 72 hours, obtain polydichlorophosphazene elastomerics, the elastomeric general formula of described polydichlorophosphazene is as shown in formula II:
Wherein, i is integer;
Step 2, under protection of inert gas, the obtained polydichlorophosphazene elastomerics of step one and the first organic solvent is added in another reactor, be mixed with the polydichlorophosphazene elastomer solution that concentration is 2 ~ 20wt%, first in described polydichlorophosphazene elastomer solution, drip hydrophobic alkyl secondary amine and organic bases, react under room temperature condition after 2 ~ 24 hours and add water-soluble Amino Terminated polyether(ATPE) again, react 2 ~ 24 hours at ambient temperature again, wherein, described polydichlorophosphazene elastomerics, described water-soluble Amino Terminated polyether(ATPE), the mol ratio of described hydrophobic alkyl secondary amine and described organic bases is 1:1 ~ 2:1 ~ 2:1 ~ 4, afterwards the reaction soln obtained is precipitated to obtain described symmetrical ordered structure pectination amphipathic nature polyalcohol.
5. the preparation method of symmetrical ordered structure pectination amphipathic nature polyalcohol according to claim 4, is characterized in that, the condition of vacuum high-temperature described in step one specifically refers to that vacuum tightness is 20 ~ 2000Pa, and temperature of reaction is 200 ~ 260 DEG C; Preferably, the elastomeric number-average molecular weight of described polydichlorophosphazene obtained in step one is 0.5-2 ten thousand.
6. the preparation method of symmetrical ordered structure pectination amphipathic nature polyalcohol according to claim 4, is characterized in that, the general molecular formula of the water-soluble Amino Terminated polyether(ATPE) described in step 2 is NH
2(CH
2cH
2o)
knH
2, wherein k is the integer of 400 ~ 2000; The general molecular formula of the secondary amine of hydrophobic alkyl described in step 2 is CH
3(CH
2)
m(NH) (CH
2)
ncH
3, wherein, m, n are the integer of 2 ~ 18; Preferably, the value of m and n is identical.
7. the polymeric hollow fibre separatory membrane of a super hydrophilic modifying, it is characterized in that, described polymeric hollow fibre separatory membrane comprises fluoropolymer resin and above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, and the polymeric hollow fibre separation membrane surface water contact angle of described super hydrophilic modifying is below 20 °.
8. the polymeric hollow fibre separatory membrane of super hydrophilic modifying according to claim 7, is characterized in that, the mass ratio of described fluoropolymer resin and described symmetrical ordered structure pectination amphipathic nature polyalcohol is 5:1 ~ 1:1; Preferably, the polymeric hollow fibre separation membrane surface water contact angle of described super hydrophilic modifying is 0 °.
9. the polymeric hollow fibre separatory membrane of super hydrophilic modifying according to claim 7, is characterized in that, described fluoropolymer resin is any one in polysulfones, polyethersulfone, polyvinylidene difluoride (PVDF), polyacrylonitrile, polyvinyl chloride.
10. a preparation method for the polymeric hollow fibre separatory membrane of the arbitrary described super hydrophilic modifying of claim 7-9, is characterized in that, comprise the steps:
The preparation process of preparation liquid, mixes fluoropolymer resin, above-mentioned symmetrical ordered structure pectination amphipathic nature polyalcohol, film for additive and the second organic solvent, at 10 ~ 90 DEG C, is uniformly mixed dissolving; After solute dissolves completely, filter cleaner, obtains polymer resin solution, then obtains preparation liquid with after rare gas element deaeration 6 ~ 48h;
Masking step, extrudes immersion precipitation liquid by the described preparation liquid obtained from spinning nozzle, and form nascent fibre, after abundant rinsing, taking-up is dried, thus the polymeric hollow fibre separatory membrane of obtained described super hydrophilic modifying;
Preferably, in the preparation process of described preparation liquid, the proportioning of the described fluoropolymer resin in the preparation liquid obtained, described symmetrical ordered structure pectination amphipathic nature polyalcohol, described film for additive and described second organic solvent is: the massfraction of described fluoropolymer resin is 15 ~ 25%, the massfraction of described symmetrical ordered structure pectination amphipathic nature polyalcohol is 5 ~ 15%, the massfraction of described film for additive is 1 ~ 20%, and the massfraction of described second organic solvent is 50 ~ 70%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112808022A (en) * | 2020-12-31 | 2021-05-18 | 太原科技大学 | Polyvinyl amine membrane with hydrophilic and hydrophobic functional groups and preparation method and application thereof |
| CN115873170A (en) * | 2022-10-23 | 2023-03-31 | 北京化工大学 | Preparation of fluorine-containing porous material and nano-microsphere from amphiphilic polyphosphazene stable fluorine-containing emulsion |
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| EP0425268A2 (en) * | 1989-10-27 | 1991-05-02 | Teijin Limited | Phosphazene polymer carrier for biologically active substance |
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| EP0425268A2 (en) * | 1989-10-27 | 1991-05-02 | Teijin Limited | Phosphazene polymer carrier for biologically active substance |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112808022A (en) * | 2020-12-31 | 2021-05-18 | 太原科技大学 | Polyvinyl amine membrane with hydrophilic and hydrophobic functional groups and preparation method and application thereof |
| CN112808022B (en) * | 2020-12-31 | 2022-10-21 | 太原科技大学 | Polyvinyl amine membrane with hydrophilic and hydrophobic functional groups and preparation method and application thereof |
| CN115873170A (en) * | 2022-10-23 | 2023-03-31 | 北京化工大学 | Preparation of fluorine-containing porous material and nano-microsphere from amphiphilic polyphosphazene stable fluorine-containing emulsion |
| CN115873170B (en) * | 2022-10-23 | 2024-04-26 | 河北开滦航橡新材料有限公司 | Preparation of fluorine-containing porous material and nano microsphere by amphiphilic polyphosphazene stabilized fluorine-containing emulsion |
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