CN101439269A - Method for preparing thermoplastic polyurethane elastic hollow fiber membrane - Google Patents
Method for preparing thermoplastic polyurethane elastic hollow fiber membrane Download PDFInfo
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- CN101439269A CN101439269A CNA2008101363651A CN200810136365A CN101439269A CN 101439269 A CN101439269 A CN 101439269A CN A2008101363651 A CNA2008101363651 A CN A2008101363651A CN 200810136365 A CN200810136365 A CN 200810136365A CN 101439269 A CN101439269 A CN 101439269A
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Abstract
The invention discloses a preparation method for a thermoplastic polyurethane elastic hollow fibrous membrane. The method is characterized in that the technical method comprises the steps as follows: the thermoplastic polyurethane after hot-melt treatment or blending is dissolved by a strong polar solvent at the temperature of 40 and 120 DEG C and then is added with a pore former, completely dissolved and stood for 20 to 24h under the temperature at 40 and 120 DEG C for removing the tiny air bladders in the thermoplastic polyurethane; then cured membrane liquid is pressed into a filter screen for filtering by N2 and is pumped into the homocentric spinning head of two round holes by a metering pump; the inner hole of the spinning head is de-ionized water; the annular space of the outer hole of the spinning head is the membrane preparing liquid. The method has the advantages of simple technique, low dissolving temperature and less additive; moreover, the resilience of the hollow fibrous membrane is adjustable; the thermoplastic polyurethane of different hard segment contents can all carry out the preparation of membranes; the prepared elastic hollow fibrous membrane can be applied to the fields like hyperfiltration, micro-filtration and filtration of blood products.
Description
Technical field
The present invention relates to a kind of preparation method of hollow-fibre membrane, relate in particular to a kind of preparation method of thermoplastic polyurethane elastic hollow-fibre membrane.
Background technology
Nearly development decades of membrane separation technique has been widely applied to various fields such as environmental project, food, medicine, petrochemical industry rapidly.Form according to film can be divided into four classes such as flat sheet membrane, tubular membrane, hollow-fibre membrane and capillary type film.Hollow-fibre membrane has self supporting structure and makes membrane module preparation simple because the preparation method is simple, and enlarge-effect is little, and the pack completeness of unit volume inner membrance is high and used widely.The membrane material of doughnut film preparation mainly contains cellulose acetate, polyimides, polyamide, Kynoar, polysulfones, polyether sulfone, polyvinyl chloride, polyacrylonitrile, polypropylene, polyethylene etc., these materials itself belong to rigid macromolecule, and film silk The apparent phenomenon is harder.
The TPUE block copolymer that to be a class be made up of soft section and hard section, soft section at room temperature is in elastomeric state, can produce very big elongation strain during stretching, and has good resilience; And hard section is given elastomer with performances such as higher-strength, rigidity and high-melting-points, for soft section elongation strain and resilience provide node.Thermoplastic polyurethane makes it have many characteristics such as high resilience, high-strength, wear-resisting, chemicals-resistant, weather-proof, UV resistant irradiation ability with its unique chemical structure, is extensive use of in industries such as automobile, process hides, electric wire and cable.Tianjin University of Technology's peace woods employing fibre-grade polyurethane such as (200610013868.0) is main body phase membrane material, polyacrylonitrile, Kynoar are decentralized photo, mode with the melt spinning-pull stretching pore has prepared hollow-fibre membrane, elastic recovery rate is low behind the prepared film silk of this method poor heat stability, the high temperature deformation, porosity is low, and spinning technology parameter is difficult to control.In order to continue to keep the high resiliency of thermoplastic polyurethane, improve the self-supporting of thermoplastic polyurethane, the present invention adopts the thermoplastic polyurethane hot melt processing of high-hard section content or the thermoplastic polyurethane that hangs down hard segment content is strengthened with polyblend, and intensive polar solvent dissolving back adopts the preparation technology of dry-jet wet-spinning to prepare porous thermoplastic elastic polyurethane hollow-fibre membrane.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of thermoplastic polyurethane elastic hollow-fibre membrane, the hollow-fibre membrane that this preparation method makes has good resilience and pressure deformation recovery.
The present invention is achieved like this, and it is characterized in that the process step is:
(1) mass percent of each ingredients constitute total amount is in the casting solution: thermoplastic polyurethane 15～30%, decentralized photo 6～15%, pore former 3%～15%, intensive polar solvent 40～76%, the thermoplastic polyurethane particle of weighing high-hard section content, obtain the fine granularity thing with the section of single screw extrusion machine hot melt, hot melting temperature is 150 ℃～280 ℃, single screw extrusion machine is extruded the fritter polymer that obtains to be mixed with intensive polar solvent, mixture is stirred 2-3h down in 40 ℃～120 ℃, add pore former again, stir 3-4h again, making wherein, polymer dissolves the preparation liquid that becomes homogeneous phase fully;
(2) mass percent of each ingredients constitute total amount is in the casting solution: thermoplastic polyurethane 15～30%, decentralized photo 6～15%, pore former 3%～15%, intensive polar solvent 40～76%, the thermoplastic polyurethane of the low hard segment content of weighing, add intensive polar solvent with a kind of mixing back in polysulfones, polyether sulfone, poly aryl ether arone, the polyacrylonitrile, mixture is stirred 2～3h down in 40 ℃～120 ℃, add pore former again, stir 3～4h again, making wherein, polymer dissolves the preparation liquid that becomes homogeneous phase fully;
(3) preparation liquid with step 1 and step 2 gained leaves standstill 20～24h under 40 ℃～120 ℃, sloughs micro-bubble in the preparation liquid, then will be through the preparation liquid N of overcuring
2Be pressed into screen pack and filter, squeeze in the concentric spinneret in circular two holes through measuring pump, the spinneret endoporus is that the outer orifice ring crack of deionized water, spinneret is a preparation liquid;
(4) preparation liquid of extruding from spinneret forms the nascent state film at air evaporation 15s～20s earlier, is introduced in the running water gel solidification film forming then by guide wheel;
(5) step 4 is prepared hollow-fibre membrane is on the guide wheel of 40～60cm around diameter, and behind the immersion 24h, cutting obtains the finished product hollow-fibre membrane in water.
Intensive polar solvent of the present invention is a kind of of N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide or their mixture.
Pore former of the present invention is a kind of of triethyl phosphate, glacial acetic acid, ethyl acetate, methyl acetate, ethylenediamine, polyvinylpyrrolidone, polyethylene glycol, sodium phosphate trimer, polyvinyl alcohol or their mixture.
Hollow-fibre membrane spinning technology parameter of the present invention is: spinning temperature is 30 ℃～80 ℃, extruded velocity 10ml/mim～30ml/min, at air evaporation time 15s～20s, winding speed is 10m/min～40m/min, and inner gel is bathed flow velocity 14ml/mim～20ml/min.
Advantage of the present invention is: technology is simple, solution temperature is low, and additive is few, and the doughnut film resilience is adjustable, the thermoplastic polyurethane of different hard segment contents all can carry out the preparation of film, and prepared elastic hollow tunica fibrosa can be applicable to fields such as ultrafiltration, micro-filtration, blood product filtration.
The specific embodiment
Embodiment one:
Take by weighing 200g hardness 93ShoreA, hard segment content is that 55% graininess thermoplastic polyurethane is made the polyurethane section under on the single screw extrusion machine 190 ℃, with above-mentioned section resin after vacuum drying, add the 490ml dimethyl formamide solution, stir down 3～4h at 80 ℃, treat dissolving fully after, add again after 50g polyvinylpyrrolidone (K30) stirs 3～4h, dissolving fully, leave standstill 24h, use N
2Pressurization by behind the strainer filtering of 0.01 μ m, is squeezed into spinneret by measuring pump with solution, earlier through the air gap, enters gel solidification film forming in the gel groove then.The thermoplastic polyurethane elastic hollow-fibre membrane that forms, internal diameter 0.46 μ m～0.89 μ m, external diameter 0.68 μ m～1.4 μ m, water flux is 160L/m
2.h (0.1Mpa), percentage elongation 400%, the aperture is 0.3 μ m.
Embodiment two:
Take by weighing 200g hardness 85ShoreA respectively, hard segment content is 45% graininess thermoplastic polyurethane and 100g polyacrylonitrile, and both mix the back and add the 600ml dimethylacetylamide, 70 ℃ of following stirring and dissolving 3h, add the 40g sodium phosphate trimer again and stir 4h, leave standstill 24h after treating to dissolve fully, use N
2Pressurization by behind the strainer filtering of 0.01 μ m, is squeezed into spinneret by measuring pump with solution, earlier through the air gap, enters gel solidification film forming in the gel groove then.The thermoplastic polyurethane elastic hollow-fibre membrane of prepared blending and modifying, water flux are 180L/m
2.h (0.2MPa), percentage elongation 250%, the aperture is 0.25 μ m.
Embodiment three;
Take by weighing 200g hardness 78ShoreA respectively, hard segment content is 35% granular thermoplastic polyurethane and 40g polysulfones, both mix the back and add the 700ml dimethylacetamide solution, stir 3～4h down at 90 ℃, after treating dissolving fully, add after polyethylene glycol (400) stirs 3～4h, dissolving fully according to 7% amount again, leave standstill 24h, use N
2Pressurization by behind the strainer filtering of 0.01 μ m, is squeezed into spinneret by measuring pump with solution, earlier through the air gap, enters gel solidification film forming in the gel groove then.The thermoplastic polyurethane elastic hollow-fibre membrane that forms, internal diameter 0.36 μ m～0.85 μ m, external diameter 0.60 μ m～1.2 μ m water fluxes are 200L/m
2.h (0.1MPa), percentage elongation 350%, the aperture is 0.4 μ m.
Claims (3)
1, a kind of preparation method of thermoplastic polyurethane elastic hollow-fibre membrane is characterized in that the process step is:
(1) mass percent of each ingredients constitute total amount is in the casting solution: thermoplastic polyurethane 15～30%, decentralized photo 6～15%, pore former 3%～15%, intensive polar solvent 40～76%, the thermoplastic polyurethane particle of weighing high-hard section content, obtain the fine granularity thing with the section of single screw extrusion machine hot melt, hot melting temperature is 150 ℃～280 ℃, single screw extrusion machine is extruded the fritter polymer that obtains to be mixed with intensive polar solvent, mixture is stirred 2-3h down in 40 ℃～120 ℃, add pore former again, stir 3-4h again, making wherein, polymer dissolves the preparation liquid that becomes homogeneous phase fully;
(2) mass percent of each ingredients constitute total amount is in the casting solution: thermoplastic polyurethane 15～30%, decentralized photo 6～15%, pore former 3%～15%, intensive polar solvent 40～76%, a kind of mixing back in the thermoplastic polyurethane of the low hard segment content of weighing and polysulfones, polyether sulfone, poly aryl ether arone, the polyacrylonitrile adds intensive polar solvent, mixture is stirred 2-3h down in 40 ℃～120 ℃, add pore former again, stir 3-4h again, making wherein, polymer dissolves the preparation liquid that becomes homogeneous phase fully;
(3) preparation liquid with step 1 and step 2 gained leaves standstill 20-24h under 40 ℃～120 ℃, sloughs the micro-bubble in the preparation liquid, then will be through the preparation liquid N of overcuring
2Be pressed into screen pack and filter, squeeze in the concentric spinneret in circular two holes through measuring pump, the spinneret endoporus is that the outer orifice ring crack of deionized water, spinneret is a preparation liquid;
(4) preparation liquid of extruding from spinneret forms the nascent state film at air evaporation 15s～20s earlier, is introduced in the running water gel solidification film forming then by guide wheel;
(5) step 4 is prepared hollow-fibre membrane is on the guide wheel of 40-60cm around diameter, and behind the immersion 24h, cutting obtains the finished product hollow-fibre membrane in water.
2, the preparation method of a kind of thermoplastic polyurethane elastic hollow-fibre membrane according to claim 1 is characterized in that described intensive polar solvent is a kind of of N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide or their mixture.
3, the preparation method of a kind of thermoplastic polyurethane elastic hollow-fibre membrane according to claim 1 is characterized in that described pore former is a kind of of triethyl phosphate, glacial acetic acid, ethyl acetate, methyl acetate, ethylenediamine, polyvinylpyrrolidone, polyethylene glycol, sodium phosphate trimer, polyvinyl alcohol or their mixture.
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| CNA2008101363651A CN101439269A (en) | 2008-12-04 | 2008-12-04 | Method for preparing thermoplastic polyurethane elastic hollow fiber membrane |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851361A (en) * | 2010-05-25 | 2010-10-06 | 南昌航空大学 | Hollow fiber damping material of nitrile butadiene rubber and preparation method thereof |
| CN102000515A (en) * | 2010-09-10 | 2011-04-06 | 惠州七芯膜净化环保有限公司 | Thermoplastic polyurethane hollow fiber membrane and preparation method thereof |
| CN102295323A (en) * | 2011-06-16 | 2011-12-28 | 天津工业大学 | Water processing method |
| CN101623604B (en) * | 2009-07-29 | 2012-08-29 | 四川大学 | Preparation method of hollow-fiber membrane with high intensity and high flux and additive thereof |
| CN103143267A (en) * | 2013-03-06 | 2013-06-12 | 宁波净源膜科技有限公司 | Preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane |
| CN103143268A (en) * | 2013-03-06 | 2013-06-12 | 宁波净源膜科技有限公司 | Preparation method of polyvinylidene fluoride/polyurethane/polyvinyl chloride blend hollow fiber separation membrane |
| CN107708760A (en) * | 2015-06-17 | 2018-02-16 | 旭化成医疗株式会社 | Blood processing filter filter element, blood processing filter and blood processing |
| CN109320754A (en) * | 2018-10-16 | 2019-02-12 | 张静娟 | A kind of environment-friendly preparation method thereof of cellular polyurethane carrier |
| CN110479122A (en) * | 2019-09-03 | 2019-11-22 | 贵州省材料产业技术研究院 | A kind of preparation method of porous polymer in-situ micro-fibril water-oil separating material |
| CN111185104A (en) * | 2020-01-09 | 2020-05-22 | 东华大学 | Composite forward osmosis membrane and preparation method and application thereof |
| CN114733364A (en) * | 2021-01-07 | 2022-07-12 | 杭州费尔新材料有限公司 | Preparation method of low-impurity polyolefin hollow fiber membrane |
-
2008
- 2008-12-04 CN CNA2008101363651A patent/CN101439269A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623604B (en) * | 2009-07-29 | 2012-08-29 | 四川大学 | Preparation method of hollow-fiber membrane with high intensity and high flux and additive thereof |
| CN101851361A (en) * | 2010-05-25 | 2010-10-06 | 南昌航空大学 | Hollow fiber damping material of nitrile butadiene rubber and preparation method thereof |
| CN102000515A (en) * | 2010-09-10 | 2011-04-06 | 惠州七芯膜净化环保有限公司 | Thermoplastic polyurethane hollow fiber membrane and preparation method thereof |
| CN102000515B (en) * | 2010-09-10 | 2013-03-20 | 惠州七芯膜净化环保有限公司 | Thermoplastic polyurethane hollow fiber membrane and preparation method thereof |
| CN102295323A (en) * | 2011-06-16 | 2011-12-28 | 天津工业大学 | Water processing method |
| CN102295323B (en) * | 2011-06-16 | 2013-06-05 | 天津工业大学 | Water processing method |
| CN103143268B (en) * | 2013-03-06 | 2015-08-12 | 浙江净源膜科技有限公司 | The preparation method of polyvinylidene fluoride/polyurethane/polyvinyl chloride blend hollow fiber separation membrane |
| CN103143268A (en) * | 2013-03-06 | 2013-06-12 | 宁波净源膜科技有限公司 | Preparation method of polyvinylidene fluoride/polyurethane/polyvinyl chloride blend hollow fiber separation membrane |
| CN103143267A (en) * | 2013-03-06 | 2013-06-12 | 宁波净源膜科技有限公司 | Preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane |
| CN103143267B (en) * | 2013-03-06 | 2015-08-12 | 浙江净源膜科技有限公司 | The preparation method of polysulfone/polyurethane/polyvinyl chloride blend hollow fiber separation membrane |
| CN107708760A (en) * | 2015-06-17 | 2018-02-16 | 旭化成医疗株式会社 | Blood processing filter filter element, blood processing filter and blood processing |
| CN109320754A (en) * | 2018-10-16 | 2019-02-12 | 张静娟 | A kind of environment-friendly preparation method thereof of cellular polyurethane carrier |
| CN110479122A (en) * | 2019-09-03 | 2019-11-22 | 贵州省材料产业技术研究院 | A kind of preparation method of porous polymer in-situ micro-fibril water-oil separating material |
| CN110479122B (en) * | 2019-09-03 | 2021-09-21 | 贵州省材料产业技术研究院 | Preparation method of porous polymer in-situ microfiber oil-water separation material |
| CN111185104A (en) * | 2020-01-09 | 2020-05-22 | 东华大学 | Composite forward osmosis membrane and preparation method and application thereof |
| CN114733364A (en) * | 2021-01-07 | 2022-07-12 | 杭州费尔新材料有限公司 | Preparation method of low-impurity polyolefin hollow fiber membrane |
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Open date: 20090527 |