CN102000515A - Thermoplastic polyurethane hollow fiber membrane and preparation method thereof - Google Patents
Thermoplastic polyurethane hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN102000515A CN102000515A CN2010102792613A CN201010279261A CN102000515A CN 102000515 A CN102000515 A CN 102000515A CN 2010102792613 A CN2010102792613 A CN 2010102792613A CN 201010279261 A CN201010279261 A CN 201010279261A CN 102000515 A CN102000515 A CN 102000515A
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- 239000012528 membrane Substances 0.000 title claims abstract description 59
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 54
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000012510 hollow fiber Substances 0.000 title abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 47
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 230000004907 flux Effects 0.000 claims abstract description 14
- 238000002145 thermally induced phase separation Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 34
- 235000012489 doughnuts Nutrition 0.000 claims description 27
- 239000003085 diluting agent Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 18
- -1 pentaerythritol ester Chemical class 0.000 claims description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008188 pellet Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 230000004927 fusion Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- GQJDFTIOKVGUOF-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO GQJDFTIOKVGUOF-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 229920002635 polyurethane Polymers 0.000 abstract description 10
- 239000004814 polyurethane Substances 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 235000020188 drinking water Nutrition 0.000 abstract description 3
- 239000003651 drinking water Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000008399 tap water Substances 0.000 abstract description 3
- 235000020679 tap water Nutrition 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 2
- 230000008018 melting Effects 0.000 abstract 2
- 239000013535 sea water Substances 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 14
- 238000005469 granulation Methods 0.000 description 11
- 230000003179 granulation Effects 0.000 description 11
- 238000009987 spinning Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000010618 wire wrap Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates 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
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a thermoplastic polyurethane hollow fiber membrane and a preparation method thereof. The hollow fiber membrane is made of polyurethane and prepared by adopting a thermally induced phase separation process. The preparation method comprises the following steps of: mixing thermoplastic polyurethane, thinner, inorganic pore-forming agent and antioxidant uniformly by using a high-speed stirrer, melting and extruding the mixture into granules by using a double-screw extruder, then melting and extruding the granules into hollow fibers by using a single-screw extruder, performing cooling molding, and finally extracting the thinner and the inorganic pore-forming agent in the hollow fibers. The prepared thermoplastic polyurethane hollow fiber membrane has the advantages of high flux, tensile strength and compressive strength, good flexibility of membrane silks, high elongation of the membrane silks at break, good chemical tolerance, permanent hydrophilic property, dry storage and the like. The fiber membrane can be applied to filtration of household and commercial drinking water, filtration and purification of brewed wine, food and medicaments, municipal tap water and sewage treatment, industrial sewage treatment, sea water desalinization pretreatment and the like.
Description
Technical field
The present invention relates to a kind of thermoplastic polyurethane hollow-fibre membrane and preparation method thereof-thermally induced phase separation.
Background technology
Industrial in recent years develop rapidly, but cause the pollution of environment also more and more serious simultaneously, factory's exhaust gas discharged, waste liquid, solid slag are very big to the pollution of surrounding environment, and wherein the waste liquid of Chan Shenging is very serious to the pollution of water, and serious threat is to existent environment of people.Membrane separation technique develops over year rapidly at nearly twenty or thirty, compare with traditional separation method, membrane separating method has advantages such as efficiency is low, technology simple, environmentally safe, membrane separation technique is widely used in the wastewater treatment of industry such as chemical industry, food, medicine, electronics, electric power, municipal tap water and sewage disposal, family expenses and commercial drinking water filtration treatment, aspects such as desalinization.Be used to make the material of diffusion barrier,, develop into polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, polysulfones, Kynoar, polyether sulfone etc. from cellulose acetate.The film manufacturing process has non-solvent to cause to be separated, melt spinning-stretching hole forming method and thermally induced phase separation.
Plastic polyurethane also is polyurethane elastomer, has not only had the characteristic of plastics but also has had the characteristic of rubber concurrently, have other plastic material incomparable good toughness, shock-resistant, good springiness, elongation at break height, elongation at break is more than 500%; Have simultaneously other elastomeric material incomparable high strength, tensile strength can reach more than the 25MPa; Have characteristics such as wear-resisting, cold-resistant, oil resistant, water-fast, ageing-resistant, weatherability, ozone resistance is good, chemical proofing is good.Thermoplastic polyurethane has good processing properties, can extrude as plastic material, technological forming such as injection.The price of thermoplastic polyurethane is more cheap than polyether sulfone, Kynoar, is fit to very much the preparation hollow-fibre membrane.Chinese patent publication number CN 101306329A has introduced a kind of preparation method of polyurethane hollow fiber filter membrane, obtain polyurethane prepolymer after polyalcohol, isocyanates and pre-polymerization additive stirred, generate the polyurethane film-forming glue to wherein adding solvent, chain extender and additive again, use setting medium in solvent and the additive preparation simultaneously, prepare polyurethane hollow fiber filter membrane with dried-wet spinning silk technology.This method needs polyurethane preformed polymer, and processing step is complicated, and doing of adopting-wet method is that non-solvent causes phase separation method technology, and the doughnut film strength of preparation is relatively poor.China Patent No. ZL200610013868.0 has introduced a kind of polyurethane comixing hollow-fibre membrane and manufacture method thereof, polyurethane and polyolefin polymers (comprising Kynoar and polyacrylonitrile) blend, and can add inorganic compound (calcium carbonate, silica or simple substance carbon), as the blend extrusion equipment, adopt the method for melt spinning-stretching pore-forming to make the polyurethane comixing hollow-fibre membrane with double screw extruder.Do not need any solvent and additive in the film-forming process, manufacture method is simple, and relative cost is lower, environmentally safe.Doughnut film strength with the preparation of the method for melt spinning-stretching pore-forming is higher, but because tear by pulling force in the hole on the wall forms, the out-of-shape in hole, the size in hole and skewness, the size in hole is difficult to control.
Thermally induced phase separation technology is the manufacture method of a kind of hollow-fibre membrane of getting up of developed recently, it is at high temperature polymer and diluent or inorganic pore former etc. to be mixed, form homogeneous phase solution, be extruded into doughnut then, in cooling procedure, system can take place that solid-liquid is separated and liquid-liquid phase separation.After phase-splitting, it is continuous phase that system forms with the polymer, and diluent and inorganic pore former are the two phase structure of decentralized photo, at this moment select suitable extractant that diluent and inorganic pore former are extracted again.With the hollow-fibre membrane of thermally induced phase separation technology preparation, additive diluent and inorganic pore former all are extracted out, and the hollow-fibre membrane after the last moulding only contains polymer, so the film strength height, the porosity height of film, flux height.Thermoplastic polyurethane is made hollow-fibre membrane and is adopted non-solvent to cause the existing patent report of spinning technique of phase separation method and melt spinning-stretching hole forming method, does not appear in the newspapers but prepare the thermoplastic polyurethane hollow-fibre membrane with thermally induced phase separation technology.The present invention adopts thermally induced phase separation technology to prepare the thermoplastic polyurethane hollow-fibre membrane, and the hollow-fibre membrane flexibility that makes is good, intensity height simultaneously, and porosity height, flux are big.
Summary of the invention
One object of the present invention is to provide a kind of thermoplastic polyurethane hollow-fibre membrane, and the characteristics of this hollow-fibre membrane maximum are to have higher intensity to have good flexibility simultaneously.
A kind of thermoplastic polyurethane hollow-fibre membrane, it comprises the component of following percetage by weight:
Thermoplastic polyurethane: 99.5～99.9%
Antioxidant: 0.1～0.5%.
Preferably, described thermoplastic polyurethane is the extrusion grade resin.
Preferably, described antioxidant is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecanol ester, 1,3,5-trimethyl-2,4, in 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites one or more.
Another object of the present invention provides a kind of thermally induced phase separation preparation technology of thermoplastic polyurethane hollow-fibre membrane, and preparation process is as follows:
(1) thermoplastic polyurethane, diluent, inorganic pore former, antioxidant are mixed, and with the material fusion in 175～210 ℃ that stirs, and extrude and make pellet;
(2) then, described pellet 170～230 ℃ of fusions, and is extruded into doughnut, enters 25～70 ℃ tank cooling forming then;
(3) last, add an amount of diluent extractant and inorganic pore former extractant respectively the diluent and the inorganic pore former of cooled doughnut the inside are extracted, obtain the thermoplastic polyurethane hollow-fibre membrane.
Described preparation raw material comprises following components in weight percentage:
Thermoplastic polyurethane: 30～55%
Diluent: 15～45%
Inorganic pore former: 0～30%
Antioxidant: 0.1～0.5%.
Preferably, described diluent is selected from one or more in o-phthalic acid dibutyl ester, diisooctyl phthalate, dibutyl phthalate, repefral, phthalic acid two isodecyl fat, dioctyl adipate, the epoxidized soybean oil.
Preferably, described inorganic pore former is selected from one or more in nano-calcium carbonate, gas phase nano silica, nano zine oxide, the nanomete talc powder.
Preferably, described diluent extractant is selected from one or more in ethanol, n-hexane, cyclohexane, the carrene.
Preferably, described inorganic pore former extractant is selected from one or more in hydrochloric acid, sulfuric acid, NaOH, the potassium hydroxide.
Thermoplastic polyurethane hollow-fibre membrane of the present invention adopts the preparation of thermally induced phase separation technology, cause phase separation method technology with traditional non-solvent and melt spinning-stretching hole forming method technology is compared, the doughnut film-strength of thermally induced phase separation preparation is higher, flux is higher, pore size and being more evenly distributed.The present invention adopts the first granulation technology of extrusion molding hollow-fibre membrane again, on the one hand, by the double screw extruder granulation mainly be earlier to material carry out mixing evenly, on the other hand, the product size of extruding by single screw extrusion machine is more stable, and particularly nano level inorganic pore former is not easy to disperse because particle diameter is little, it is more even to adopt first process for granulating that inorganic pore former is disperseed, and the pore size distribution of the hollow-fibre membrane of preparation is more even; And, adopt single screw extrusion machine to make the material of extruding more stable, the inside/outside diameter size of the hollow-fibre membrane of moulding is more even.
Simultaneously, the hot strength of the thermoplastic polyurethane hollow-fibre membrane of the present invention's preparation is 7.5～22MPa; The flexibility of hollow-fibre membrane is good, and elongation at break is 200～350%; Flux height, pure water flux are 500～2750L/M
2H (0.1MPa, 25 ℃); Pore size and being evenly distributed, pore size is controlled, bubble point pressure 0.20～0.36MPa.It is good that the polyurethane hollow fiber film of the present invention preparation has a chemical-resistance, cleans easily; Need not add the hydrophilic modifying agent, have permanent hydrophilic, can the dry state preservation etc. advantage.The thermoplastic polyurethane hollow-fibre membrane of the present invention's preparation can be applied to the filtration treatment and the purification of family expenses and commercial drinking water filtration treatment, wine brewing, food and medicine, municipal tap water and sewage disposal, trade effluent is handled, the aspects such as pre-treatment of desalinization.
The specific embodiment
The invention provides a kind of thermoplastic polyurethane hollow-fibre membrane, it comprises the component of following percetage by weight: thermoplastic polyurethane: 99.5～99.9% and antioxidant: 0.1～0.5%.
Wherein, described thermoplastic polyurethane is the extrusion grade resin.Described antioxidant is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecanol ester, 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
The present invention adopts thermally induced phase separation to prepare described thermoplastic polyurethane hollow-fibre membrane, and preparation process comprises the steps:
(1) thermoplastic polyurethane, diluent, inorganic pore former, antioxidant are mixed, and with the material fusion in 175～210 ℃ that stirs, and extrude and make pellet;
(2) then, described pellet 170～230 ℃ of fusions, and is extruded into doughnut, enters 25～70 ℃ tank cooling forming then;
(3) last, add an amount of diluent extractant and inorganic pore former extractant respectively the diluent and the inorganic pore former of cooled doughnut the inside are extracted, obtain the thermoplastic polyurethane hollow-fibre membrane.
In step (1), the fusion in double screw extruder of the material of described mixing, and extrude and make pellet.
In step (2), described pellet is in the single screw extrusion machine fusion, and extrudes and make doughnut.
Wherein, described preparation raw material comprises following components in weight percentage: thermoplastic polyurethane: 30～55%; Diluent: 15～45%; Inorganic pore former: 0～30%; Antioxidant: 0.1～0.5%.
Preferably, the draw ratio of described double screw extruder is 32: 1 (draw ratio: spiro rod length and diameter ratio).The draw ratio of described single screw extrusion machine is 24: 1 (draw ratio: spiro rod length and diameter ratio).
The present invention includes the thermoplastic polyurethane hollow-fibre membrane of thermoplastic polyurethane by adopting the thermally induced phase separation preparation, in preparation process, adopted the technology of extrusion molding after the first granulation, double screw extruder is made pellet and single screw extrusion machine is extruded into doughnut with passing through in regular turn behind the described raw material blending, carry out cooling forming again and extract processing, to obtain thermoplastic polyurethane hollow-fibre membrane finished product.
With specific embodiment the present invention further is illustrated below.
Embodiment 1: take by weighing 43% thermoplastic polyurethane by weight, 24% o-phthalic acid dibutyl ester, 11% dioctyl adipate, 21.7% nano-calcium carbonate, 0.1% 4 [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2% tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, mix with mixer, the material that mixes is through 200 ℃, draw ratio is that 32: 1 double screw extruder melt extrudes granulation, material after the granulation is through 210 ℃, draw ratio is that 24: 1 single screw extrusion machine melt extrudes, through the bushing type spinning head, the spinning head central tube feeds nitrogen, be extruded into doughnut, air distance through 15cm enters 40 ℃ of tank cooling formings then, and the doughnut after the moulding is collected with wire wrapping wheel.Doughnut after the collection extracts diluent o-phthalic acid dibutyl ester, dioctyl adipate and inorganic pore former calcium carbonate with ethanol and hydrochloric acid respectively, the external diameter 1.25mm of the thermoplastic polyurethane hollow-fibre membrane that makes, internal diameter 0.63mm, porosity 73%, bubble point pressure is 0.29MPa, pure water flux is 1350L/m2hr (0.1MPa, 25 ℃), and hot strength 16.8MPa, extension at break are 240%.
Embodiment 2: take by weighing 50% thermoplastic polyurethane by weight, 25% o-phthalic acid dibutyl ester, 10% dibutyl phthalate, 14.7% nano-calcium carbonate, 0.1% 4 [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2% tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, mix with mixer, the material that mixes is through 210 ℃, draw ratio is that 32: 1 double screw extruder melt extrudes granulation, material after the granulation is through 215 ℃, draw ratio is that 24: 1 single screw extrusion machine melt extrudes, through the bushing type spinning head, the spinning head central tube feeds nitrogen, be extruded into doughnut, air distance through 15cm enters 30 ℃ of tank cooling formings then, and the doughnut after the moulding is collected with wire wrapping wheel.Doughnut after the collection extracts diluent o-phthalic acid dibutyl ester, dibutyl phthalate and inorganic pore former calcium carbonate with ethanol and hydrochloric acid respectively, the thermoplastic polyurethane hollow-fibre membrane external diameter 1.24mm that makes, internal diameter 0.64mm, porosity 70%, bubble point pressure is 0.30MPa, pure water flux is 1185L/m2hr (0.1MPa, 25 ℃), and hot strength 14.8MPa, extension at break are 260%.
Embodiment 3: take by weighing 40% thermoplastic polyurethane by weight, 25% diisooctyl phthalate, 15% dibutyl phthalate, 19.7% gas phase nano silica, 0.1% β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecanol ester, 0.2% tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, mix with mixer, the material that mixes is through 175 ℃, draw ratio is that 32: 1 double screw extruder melt extrudes granulation, material after the granulation is through 170 ℃, draw ratio is that 24: 1 single screw extrusion machine melt extrudes, through the bushing type spinning head, the spinning head central tube feeds nitrogen, be extruded into doughnut, air distance through 15cm enters 25 ℃ of tank cooling formings then, and the doughnut after the moulding is collected with wire wrapping wheel.Doughnut after the collection extracts diluent diisooctyl phthalate, dibutyl phthalate and inorganic pore former silica with n-hexane and NaOH respectively.The thermoplastic polyurethane hollow-fibre membrane external diameter 1.26mm that makes, internal diameter 0.64mm, porosity 75%, bubble point pressure is 0.27MPa, pure water flux is 1860L/m
2Hr (0.1MPa, 25 ℃), hot strength 12.7MPa, extension at break are 235%.
Embodiment 4: take by weighing 37% thermoplastic polyurethane by weight, 30% diisooctyl phthalate, 15% epoxidized soybean oil, 17.7% gas phase nano silica, 0.1% 4 [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2% pair of (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites, mix with mixer, the material that mixes is through 180 ℃, draw ratio is that 32: 1 double screw extruder melt extrudes granulation, material after the granulation is through 185 ℃, draw ratio is that 24: 1 single screw extrusion machine melt extrudes, through the bushing type spinning head, the spinning head central tube feeds nitrogen, be extruded into doughnut, air distance through 15cm enters 32 ℃ of tank cooling formings then, and the doughnut after the moulding is collected with wire wrapping wheel.Hollow fibre filament after the collection extracts diluent diisooctyl phthalate, epoxidized soybean oil and inorganic pore former silica with n-hexane and NaOH respectively.The thermoplastic polyurethane hollow-fibre membrane external diameter 1.23mm that makes, internal diameter 0.63mm, porosity 79%, bubble point pressure is 0.26MPa, pure water flux is 2100L/m
2Hr (0.1MPa, 25 ℃), hot strength 9.7MPa, extension at break are 220%.
Can find out from the various embodiments described above, the thermoplastic polyurethane of corresponding proportion, diluent, inorganic pore former, antioxidant etc. are added mixing in the mixer, and the material behind the mixing is extruded into doughnut through double screw extruder extruding pelletization and single screw extrusion machine in regular turn, melt temperature is controlled at respectively in 175～210 ℃ and 170～230 ℃, then it is inserted 25～70 ℃ of tanks and carry out cooling forming, at last, again the diluent and the inorganic pore former of the inside of the doughnut after the moulding are extracted, obtain the thermoplastic polyurethane hollow-fibre membrane.Adopting twin-screw and single screw extrusion machine to be extruded into doughnut again through first extruding pelletization respectively makes various raw materials mixing more even, with the aperture that reaches suitable and be evenly distributed, the hot strength and the elongation at break of the hollow-fibre membrane that assurance is obtained are higher, and water flux is also big.
Its each parameter of thermoplastic polyurethane hollow-fibre membrane by method for preparing is all in following scope: the hot strength of described hollow-fibre membrane is 7.5～22MPa, elongation at break 200～350%; Pure water flux is 500～2750L/M
2H (0.1MPa, 25 ℃); Bubble point pressure 0.20～0.36MPa.Thermoplastic polyurethane hollow-fibre membrane of the present invention is compared with existing filter membrane, and its water flux is higher, and film strength is better.Filter membrane of the present invention has pore size and is evenly distributed, and pore size is controlled, and it is good to have a chemical-resistance, cleans easily; Need not add the hydrophilic modifying agent, have permanent hydrophilic, can the dry state preservation etc. advantage.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. thermoplastic polyurethane hollow-fibre membrane, it is characterized in that: it comprises the component of following percetage by weight:
Thermoplastic polyurethane: 99.5～99.9%
Antioxidant: 0.1～0.5%.
2. according to the described thermoplastic polyurethane hollow-fibre membrane of claim 1, it is characterized in that: the hot strength of described hollow-fibre membrane is 7.5～22MPa, elongation at break 200～350%; Pure water flux is 500～2750L/M
2H (0.1MPa, 25 ℃); Bubble point pressure 0.20～0.36MPa.
3. according to the described thermoplastic polyurethane hollow-fibre membrane of claim 1, it is characterized in that described thermoplastic polyurethane is the extrusion grade resin.
4. according to the described thermoplastic polyurethane hollow-fibre membrane of claim 1, it is characterized in that: described antioxidant is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecanol ester, 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
5. the preparation method of a thermoplastic polyurethane hollow-fibre membrane adopts the thermally induced phase separation preparation, and preparation process is as follows:
(1) thermoplastic polyurethane, diluent, inorganic pore former, antioxidant are mixed, and with the material fusion in 175～210 ℃ that stirs, and extrude and make pellet;
(2) then, described pellet 170～230 ℃ of fusions, and is extruded into doughnut, enters 25～70 ℃ tank cooling forming then;
(3) last, add an amount of diluent extractant and inorganic pore former extractant respectively the diluent and the inorganic pore former of cooled doughnut the inside are extracted, obtain the thermoplastic polyurethane hollow-fibre membrane.
6. according to the described preparation method of claim 5, it is characterized in that: in step (1), the fusion in double screw extruder of the material of described mixing, and extrude and make pellet.
7. according to the described preparation method of claim 5, it is characterized in that: in step (2), described pellet is in the single screw extrusion machine fusion, and is extruded into doughnut.
8. according to the described preparation method of claim 5, it is characterized in that described preparation raw material comprises following components in weight percentage:
Thermoplastic polyurethane: 30～55%
Diluent: 15～45%
Inorganic pore former: 0～30%
Antioxidant: 0.1～0.5%.
9. according to the described preparation method of claim 5, it is characterized in that: described diluent extractant is selected from one or more in ethanol, n-hexane, cyclohexane, the carrene; Inorganic pore former extractant is selected from one or more in hydrochloric acid, sulfuric acid, NaOH, the potassium hydroxide.
10. described according to Claim 8 preparation method is characterized in that: described diluent is selected from one or more in o-phthalic acid dibutyl ester, diisooctyl phthalate, dibutyl phthalate, repefral, phthalic acid two isodecyl fat, dioctyl adipate, the epoxidized soybean oil; Described inorganic pore former is selected from one or more in nano-calcium carbonate, gas phase nano silica, nano zine oxide, the nanomete talc powder.
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| CN102343224A (en) * | 2011-08-05 | 2012-02-08 | 武汉纺织大学 | Method for forming porous polyurethane membrane |
| CN102343224B (en) * | 2011-08-05 | 2013-07-03 | 武汉纺织大学 | Method for forming porous polyurethane membrane |
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| CN105561812A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | Oxidation-resistant polyacrylonitrile ultrafiltration membrane and preparation method thereof |
| CN107406278A (en) * | 2015-05-07 | 2017-11-28 | 住友电气工业株式会社 | The method of operation and filter of filter |
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| WO2018045867A1 (en) * | 2016-09-09 | 2018-03-15 | 上海科力玛数据科技有限公司 | Composite material for air purification, preparation method therefor and application thereof |
| US10780379B2 (en) | 2016-09-09 | 2020-09-22 | Climasys DataSmart Technology CO., LTD. | Composite material for air purification, preparation method therefor and application thereof |
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| CN115957637A (en) * | 2022-12-05 | 2023-04-14 | 深圳高性能医疗器械国家研究院有限公司 | Preparation method of hollow fiber exchange membrane and hollow fiber exchange membrane |
| CN115957637B (en) * | 2022-12-05 | 2025-12-12 | 深圳高性能医疗器械国家研究院有限公司 | Preparation method of hollow fiber exchange membrane and hollow fiber exchange membrane |
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