CN101322922B - Hollow fiber film and method for producing the same - Google Patents
Hollow fiber film and method for producing the same Download PDFInfo
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- CN101322922B CN101322922B CN2008100538964A CN200810053896A CN101322922B CN 101322922 B CN101322922 B CN 101322922B CN 2008100538964 A CN2008100538964 A CN 2008100538964A CN 200810053896 A CN200810053896 A CN 200810053896A CN 101322922 B CN101322922 B CN 101322922B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/54—Polyureas; Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
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Abstract
The invention relates to a hollow fiber membrane and a manufacturing method thereof. The weight percentage prescription of the membrane forming system of the membrane is: 25 to 45 percent of polyurethane; 35 to 60 percent of compound pore-forming agent; 15 to 20 percent of organic low molecular; the sum of each component is 100 percent; wherein, the polyurethane is a fiber grade; the weight ratio of a hard section and a soft section is 1/1 to 1/5; the compound pore-forming agent is the mixture of an interface cavity pore-forming agent and a non-interface cavity pore-forming agent; the organic low molecular liquid is a good water-soluble polyurethane solvent with a high boiling point; the manufacturing method of the membrane adopts the following melt spinning technique: firstly the prescription of the invention demands the preparation of a polymer membrane forming system; then the polymer membrane forming system is poured into a mixing tank to carry out heating, reinforcing and pre-mixing with a heating temperature of 130 to 140 DEG C; the polymer membrane forming system is injected into a double screw extruder after being uniformly mixed; melt blending spinning is carried out to manufacture the membrane under the temperature of 130 to 155 DEG C; then the hollow fiber membrane is obtained after the normal working procedure of water extraction washing.
Description
Technical field
The present invention relates to a kind of technology of preparing of hollow-fibre membrane, be specially a kind of hollow-fibre membrane and manufacture method thereof with favorable elasticity function, international monopoly Main classification number plan is Int.Cl..B01D 69/00 (2006.01) I.
Background technology
Polyurethanes (being polyurethane) be a class soft/block copolymer that hard section alternately is connected to form, its soft section at room temperature is in elastomeric state, can produce very big elongation strain during stretching, and have good resilience, and hard section elongation strain and the resilience for soft section provides node.Polyurethane unique chemical structure makes it have many characteristics such as high-elastic, high-strength, heat-resisting, wear-resisting, chemicals-resistant, extensive use in industries such as automobile, shoemaking, electric wire and cable.1970, Bowen proposed the selected adsorbent that polyurethane can be used as some material, and the application of polyurethane aspect material of preparing after this causes people's attention gradually.But owing to the polyurethane structural densification, be difficult to pore-forming, so polyurethane film is mainly used in gas separation, infiltration evaporation and aspects such as inorganic metal ion separates, liquid separating film is studied less relatively.At present, solution spinning is the common technology of preparation doughnut liquid separating film, its advantage is that spinning temperature is low, easy to operate, and be easy to pore-forming, people such as Li pioneer disclose " a kind of polyurethane/inorganic particle blended composite film and method for making thereof (patent No. ZL02131196X.) ", and it adopts the solution spinning process to prepare the polyurethane/inorganic particle blended hollow fiber composite membrane with interface pore characteristics.Find after further research, the gained hollow fiber composite membrane has spring function, and respective change takes place (referring to Li pioneer in the aperture that shows as with the variation tunica fibrosa micropore of operating pressure, Xiao Changfa, composite polyurethane hollow fiber film structure and performance, macromolecule journal English edition, 23 (2005) 203-210); X.F.Li, C.F.Xiao, Structure and properties of Composite Polyurethane HollowFiber Membranes, Chinese J.Polym.Sci., 23 (2005) 203-210).But this technology need consume a large amount of solvents, easily contaminated environment, and the mechanical property of gained tunica fibrosa, and the shape in the pressure-responsive process is restorative also desirable not to the utmost.Conventional fusion or melt spinning method do not need solvent, and technological process is short, but the structure of gained tunica fibrosa comparatively fine and close usually, be difficult for pore-forming, and the difficult control in aperture; Its higher spinning temperature particularly, it is more to expend the energy, and the heat endurance for polymer and pore-foaming agent requires also comparatively strict, thereby the temperature of reduction melt spinning, with energy savings, control fenestra precision and structure well, to enhance product performance, be performance melt spinning advantage, and make it the key technology of spinning suiting doughnut.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined has following 2:
Quasi-solution of the present invention first technical problem of determining is: design a kind of hollow-fibre membrane, this film has stronger pressure sensibility and good shape memory to separation system, and has abundant and stable microcellular structure, is suitable for suitability for industrialized production and actual applying.
Quasi-solution of the present invention certainly second technical problem is: the manufacture method that designs a kind of hollow-fibre membrane; this manufacture method adopts melt spinning method to make hollow-fibre membrane; but overcome the shortcoming of its high temperature power consumption and the difficult control of fenestra; it is lower to have spinning temperature; membrane pore structure is easily controlled; technological process shortening, simple, the good product quality of masking technique; cost is lower, be suitable for characteristics such as industrial-scale production; can reduce simultaneously the solvent recovery in the solution spinning; the useful environmental protection and the saving energy have excellent industrial application foreground.
The technical scheme that the present invention solves first technical problem is: design a kind of hollow-fibre membrane, it is characterized in that the film forming system mass percent prescription of this hollow-fibre membrane is:
Polyurethane 25～45;
Composite pore-forming 35～60;
Organic low molecular liquid 15～20, each component sum is 100%,
Wherein, described polyurethane is fibre-grade, and the hard section mass ratio with soft section is 1/1～1/5; Described composite pore-forming is the mixture of hole, interface pore-foaming agent and two kinds of materials of hole, non-interface pore-foaming agent, its hole, median surface pore-foaming agent accounts for 10～30% of composite pore-forming gross mass, hole, interface pore-foaming agent is meant and the inconsistent water-insoluble inorganic particulate of described polyurethane, comprises the SiO of average grain diameter 0.01～5 μ m
2And CaCO
3In a kind of mixture of or two kinds of arbitrary proportions; Hole, non-interface pore-foaming agent is meant water-soluble substances, comprises the mixture of water-soluble inorganic particle, water-soluble polymer, water or described water-soluble substances arbitrary proportion; Described water-soluble inorganic particle comprises LiCl, the CaCl of average grain diameter 0.01～5 μ m
2, a kind of among NaCl and the KCl; Described water-soluble polymer comprises polyvinylpyrrolidone or polyethylene glycol; Described organic low molecular liquid is higher boiling, water miscible polyurethane good solvent, comprises the mixture of one or more arbitrary proportions in dimethyl formamide, dimethyl sulfoxide (DMSO) and the dimethylacetylamide.
The technical scheme that the present invention solves second technical problem is: the manufacture method that designs a kind of hollow-fibre membrane, it is characterized in that this manufacture method adopts following melt-spinning technology: at first require preparation polymer film forming system according to hollow-fibre membrane mass percent prescription of the present invention, be poured into then and heat mandatory premixture in the mixing kettle and close, 130～140 ℃ of heating-up temperatures, back injection double screw extruder is mixed, behind dissolving and melting process, under 130～155 ℃ of temperature, carry out the melt blending spinning membrane system through the hollow spinning pack, after washing operation through the water collection of conventional soln spinning again, promptly obtain described hollow-fibre membrane.
Compared with prior art, manufacture method of the present invention combines solution spinning and melt spinning technology advantage separately, after adopting a small amount of suitable organic low molecular liquid and polyurethane, composite pore-forming blend evenly, carry out melt spinning, can effectively reduce spinning temperature, for example, the melt spinning processing temperature of polyurethane film is usually about 160 ℃, and the technological temperature of melt spinning of the present invention only requires 130～155 ℃, and is easy to control.By select suitable spinneret draft than and technical process such as wash through the water collection after, can make hollow-fibre membrane with accurate pressure response and multiple micropore (comprising interface micropore and non-interface micropore) structure.This film has that elastic recovery is good, water flux is high, the variation of separation system pressure is had stronger sensitiveness and the good memory function of separating, and is suitable for suitability for industrialized production and practical application; Though the manufacture method of this hollow-fibre membrane adopts melt-spinning technology simultaneously, melt temperature is relatively low; Though adopted appropriate solvent, do not need a large amount of solvents, have the spinning line weak point, membrane pore structure is easily controlled; masking technique is simple, and easy operating need not special installation, good product quality; and can reduce the solvent recovery in the solution spinning, the useful environmental protection and the saving energy are convenient to industrializing implementation.
Description of drawings
Fig. 1 is the engineering stress one strain curve schematic diagram of a kind of embodiment of hollow-fibre membrane of the present invention (embodiment 4);
Fig. 2 is the pressure response curve schematic diagram of a kind of embodiment of hollow-fibre membrane of the present invention (embodiment 6).
The specific embodiment
Further narrate the present invention below in conjunction with embodiment:
The hollow-fibre membrane (hereinafter to be referred as hollow membrane or film) of the present invention's design, its film forming system mass percent prescription is:
Polyurethane 25～45;
Composite pore-forming 35～60;
Organic low molecular liquid 15～20, each component sum is 100%.
Polyurethane in the prescription of the present invention is basal lamina material or matrix phase.Its chemical constitution comprises soft section and hard section, and hard section is the aromatic diisocyanate that low molecular dihydroxylic alcohols or diamine connect; Soft section is polyether Glycols or polyester diol.The mass ratio of described segmented polyurethane and soft section can be selected in 1/1～1/5 scope, but the mass ratio of comparatively ideal segmented polyurethane and soft section is 1/2.Select for use all other physical and chemical index of polyurethane should reach the fibre-grade level.
The composite pore-forming that designs in the prescription of the present invention requires its decomposition temperature to be higher than spinning temperature, and final gained hollow membrane is not had physics damage or chemical damage.Particularly, described composite pore-forming is the mixture of hole, interface pore-foaming agent and two kinds of materials of hole, non-interface pore-foaming agent, its median surface pore-foaming agent accounts for 10～30% of composite pore-forming gross mass, hole, interface pore-foaming agent is meant and the inconsistent water-insoluble inorganic particulate of described polyurethane, comprises the SiO of average grain diameter 0.01～5 μ m
2And CaCO
3Deng in a kind of mixture of or two kinds of arbitrary proportions; Hole, non-interface pore-foaming agent is meant water-soluble substances, comprises the mixture of water-soluble inorganic particle, water-soluble polymer, water or described water-soluble substances arbitrary proportion; Described water-soluble inorganic particle comprises LiCl, the CaCl of average grain diameter 0.01～5 μ m
2, a kind of among NaCl and KCl etc.; Described water-soluble polymer comprises polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) etc.Be to guarantee carrying out smoothly of spinning process, can in the film forming system, add low amounts of water (generally be no more than composite pore-forming gross mass 10%), help the formation of membrane permeability microcellular structure.Test shows, in described composite pore-forming scope, for guaranteeing the permeability of gained hollow-fibre membrane, Ying Yifei interface pore-foaming agent (water-soluble components) is main pore-foaming agent composition, simultaneously, for guaranteeing that tunica fibrosa still keeps mechanical property preferably after removing non-interface pore-foaming agent, the percentage that the interface pore-foaming agent accounts for the composite pore-forming gross mass is that 10-30% is more excellent relatively.With regard to the present invention in general, increase with the composite pore-forming gross mass, the water flux of gained hollow membrane also increases, but the corresponding decline of film strength, therefore, the content of described composite pore-forming should be controlled at system (one-tenth) film system gross mass 60% in, but more satisfactory pore-foaming agent content is 35～60%.After film forming,, give the membrane interface micropore by the draw ratio of control spinning head; Remove the solubility pore-foaming agent by the mode that water collection is washed, give the non-interface of film micropore, thus the permeability that obtains having concurrently interface pore structure and non-interface pore structure hollow-fibre membrane preferably.
Design uniquely in the prescription of the present invention suitable organic low molecular liquid is arranged.This is one of key technology of the present invention.Described organic low molecular liquid should be selected higher boiling, water miscible polyurethane good solvent, thereby but plasticising polyurethane and composite pore-forming can be extruded each component in abundant blend under the temperature that the polyurethane fusing point is lower relatively, improve the spinnability of system film system.Experimental study shows that described lower temperature range is 130～155 ℃.This temperature range can reduce energy consumption 18.75～3.13% for polyurethane fusing point (160 ℃ of meters), have remarkable energy saving effect.In addition, other of described organic low molecular liquid selective require its temperature that should be higher than described spinning membrane system according to being its boiling point and decomposition temperature, and final gained hollow membrane is not had physics damage or chemical damage.According to described principle, organic low molecular liquid of the present invention specifically comprises the mixture of one or more arbitrary proportions in dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMAc) and the dimethylacetylamide (DMSO) etc.Raising along with the organic low molecular content liquid, its spinning temperature can correspondingly reduce, be easy to form micropore after the extraction, help the raising of membrane flux, but too high organic low molecular content liquid can cause the hot strength of gained film and resistance to pressure to descend to some extent, therefore, the more excellent scope of the addition of organic low molecular liquid is 15～20% of a system film system gross mass among the present invention.Although the mass ratio of polyurethane substrates and organic low molecular liquid addition is far above the situation of solwution method spinning membrane system in the system film system of the present invention prescription, but this does not influence the formation of its spinning technique and tunica fibrosa microcellular structure, opposite owing to reduced the double diffusion process of solvent one non-solvent of conventional soln method, avoided the formation of big defective membrane pore structure, the gained film strength is apparently higher than the similar film of conventional soln method gained.In addition, studies show that, after its collection flush away is removed, the raising of doughnut membrane micropore structure permeability is also had positive role though the effect of described organic low molecular liquid mainly is plasticized polymer, improves the spinnability of film forming system.Manufacture method test of the present invention shows that by behind the formulation selection organic low molecular liquid of the present invention, described spinning temperature ideal range can be reduced to 130～155 ℃, and the temperature of concrete process implementing is selected relevant with the quality percentage composition of organic low molecular liquid.Manufacture method of the present invention not only can reduce spinning temperature relatively, energy savings, make the spinning process easy operating, and owing to adopt mixing kettle to heat mandatory premixture to the film forming system to close, behind dissolving and melting process, inject double screw extruder, improved the flowability of polymerization system, enlarge the range of choice of pore-foaming agent, be convenient to industrializing implementation.
The described spring function of hollow membrane of the present invention, be mainly reflected in two aspects: the first has higher elongation at break and better elastic recovery rate, after hollow membrane is subjected to the tensile stress effect, the length of film can reach 500% of original length, and after stress removed, the length of film can revert to the original length again preferably, and (deformation removed tensile stress near after 500%, the length of film can return to former length 200% in), and flux also can revert to evc flux.This performance can effectively avoid existing fiber film material deformability relatively poor, in use stressed easy generation non-reversible deformation and problem such as break; It two is after pressing in hollow membrane is subjected to, even expansion can take place in film body, thereby the micropore size that causes the film surface increases, porosity improves, can obtain the film function of " low press filtration-high-pressure wash ", by its interior press mold assembly that constitutes, realize the on-line cleaning in the film application process easily, also can reduce the number of times that conventional chemical cleans, prolong the membrane material purpose in service life thereby reach.
The present invention has designed the manufacture method (abbreviation manufacture method) of described hollow-fibre membrane simultaneously, this manufacture method requires system polymer film forming system according to hollow-fibre membrane mass percent prescription of the present invention, and adopt following melt-spinning technology to prepare described hollow-fibre membrane: at first described polymer film forming system adding mixing kettle to be heated mandatory premixture and close, heating-up temperature is 130～140 ℃, inject double screw extruder then, reach through dissolving. behind the melting process, under 130～155 ℃ of spinning temperatures, carry out the melt blending spinning membrane system by the doughnut spinning pack, operation such as wash through the water of conventional solution spinning collection again, promptly obtain described hollow-fibre membrane.
After a small amount of suitable organic low molecular liquid of manufacture method employing of the present invention and polyurethane, the composite pore-forming blend evenly, carry out the melt spinning of relative low temperature then, combine solution spinning and melt spinning technology advantage separately, create a kind of new hollow membrane manufacture method: though adopted melt-spinning technology, spinning temperature is lower than the spinning temperature of conventional method; Though the solvent that has adopted the solution spinning to use does not need a large amount of solvents, thereby it is short to have flow process, and technology is simple, and fenestra is easily controlled and energy-saving and emission-reduction, the characteristics of protection environment.
Water collection of the present invention is washed technology and is same as prior art.Wash technical process itself with regard to water collection, do not have essential distinction with the solution spinning membrane system technology of routine.Thereby the effect of washing of the water of conventional soln spinning process that different is collection mainly is in order to make solution thread generation double diffusion process freezing film, the water collection of the present invention's design is washed the existing traditional double diffusion process of setting of operation, play the effect of stablizing and improving the tunica fibrosa pore structure, have again in order in the spinning membrane system process, fully to remove the effect of water-soluble pore-foaming agent, this water collection in conventional melt spinning film-forming process, then do not occur and wash technology.
The further feature of manufacture method of the present invention is in melt blending spinning membrane system process, and first drawn operation is carried out the water collection again and washed operation, and the draw ratio of described stretching process is 3～5 times, and the stretch processing temperature is 40～60 ℃.This process has avoided conventional melt spinning to prepare that after-drawing causes the inhomogeneity destruction of tunica fibrosa microcellular structure in the hollow membrane process.
The present invention does not address part and is applicable to prior art.
Provide several specific embodiment of the present invention below, but these specific embodiments do not constitute the restriction to claim scope of the present invention.
With hard section/soft section mass ratio is that 1/2 fibre-grade EU is the polymer substrate phase, and the quality percentage composition is 25%; Composite pore-forming is the SiO of 0.01 μ m
2The mixture of powder and PVP accounts for 60% of system gross mass, and wherein the former is hole, an interface pore-foaming agent, accounts for 30% of composite pore-forming gross mass, and the latter is hole, a non-interface pore-foaming agent, accounts for 70% of composite pore-forming gross mass; Organic low molecular liquid selects DMSO, the quality percentage composition is 15%, and above-mentioned three's mixture as the film forming system, is heated mandatory premixture through mixing kettle and closes, 130 ℃ of heating-up temperatures, after processes such as dissolving and fusion, the feeding double screw extruder carries out the melt blending spinning membrane system through the hollow spinning pack, spinneret draft is selected 3 times and 5 times than respectively, processing temperature is controlled at 130 ℃, through water fully soak the collection wash after, promptly obtain described hollow membrane.
Through check, the present embodiment draw ratio is 3 times and 5 times of gained hollow membranes under 25 ℃ of 0.1MPa and temperature, platen press mensuration water flux in adopting, and the analog value that obtains is respectively: 690 and 1130 (Lm
-2H
-1).
The proportioning of hole, embodiment 1 median surface pore-foaming agent is adjusted into 10% of pore-foaming agent gross mass, and the proportioning of hole, non-interface pore-foaming agent is adjusted into 90% of pore-foaming agent gross mass, and spinneret draft is than selecting 3, and other conditions are constant, obtain described hollow membrane.
Through check, present embodiment gained hollow membrane is under 25 ℃ of 0.1MPa and temperature, and platen press is measured water flux in adopting, and the analog value that obtains is: 1090 (Lm
-2H
-1).
With hard section/soft section mass ratio is that 1/2 fibre-grade EU is the polymer substrate phase, and the quality percentage composition is 45%; Composite pore-forming is the SiO of 0.01 μ m
2The CaCO of powder, 5 μ m
3The mixture of powder and PEG accounts for 60% of system gross mass, and wherein the above two are hole, interface pore-foaming agent, and the two mass ratio is 1/1, accounts for 30% of composite pore-forming gross mass, and the latter is hole, a non-interface pore-foaming agent, accounts for 70% of composite pore-forming gross mass; Organic low molecular liquid selects DMSO, the quality percentage composition is 20%, with above-mentioned three's mixture as the film forming system, heat mandatory premixture through mixing kettle and close, after processes such as dissolving and fusion, feed double screw extruder, carry out the melt blending spinning membrane system through the hollow spinning pack, spinneret draft is than selecting 3, processing temperature is controlled at 155 ℃, through water fully soak the collection wash after, can make described hollow membrane.
Through check, present embodiment gained hollow membrane is under 25 ℃ of 0.1MPa and temperature, and platen press is measured water flux in adopting, and the analog value that obtains is: 920 (Lm
-2H
-1).
On the basis of enforcement 2, non-interface pore-foaming agent PVP is changed into LiCl, the CaCl of 2 μ m respectively
2, NaCl and KCl particle, other conditions are constant, can make the hollow membrane of 4 kinds of prescriptions.
Through check, each hollow membrane of present embodiment gained is under 25 ℃ of 0.1MPa and temperature, and platen press is measured its water flux respectively in adopting, and the analog value that obtains is respectively: 1520,1610,1480 and 1590 (Lm
-2H
-1).
Adopt the hollow membrane that wherein adds KCl particle gained to do the strong elastic experiment, get stress strain curve (referring to Fig. 1).As can be seen from Figure 1, the elongation at break of tunica fibrosa under the tensile stress effect is bigger, can reach 500%, and deformation removes tensile stress near after 500%, the length of tunica fibrosa can return to former length 200% in.
Organic low molecular liquid among the embodiment 1 is changed to DMF, DMAc, and other conditions are constant, make hollow membrane.
Through check, present embodiment gained hollow membrane is under 25 ℃ of 0.1MPa and temperature, and platen press is measured its water flux respectively in adopting, and the analog value that obtains than embodiment 1 significant change does not take place.
Embodiment 6
Contain CaCl with what embodiment 4 made
2Hollow membrane under 25 ℃, platen press is measured its water flux under different operating pressure in adopting, and can obtain its pressure response curve (referring to Fig. 2).
The microcellular structure of hollow membrane can be assumed to be parallel cylinder pore model and aperture equalization usually, and the water flux J by this class hole can be described below with the Hagen-Poiseuille equation,
In the formula,
Be porosity, r is a pore radius, and η is a viscosity, and Δ P is an operating pressure, and d is the thickness of diffusion barrier.If adopting pure water test and permeable pressure head is that if the microcellular structure and the porosity of film do not change, then water flux is proportional to its operating pressure, is linear relationship, i.e. J=K Δ P under 0 the situation.Obviously, curvilinear motion shown in Figure 2 does not meet linear relationship.After pressing in this explanation, hollow membrane of the present invention are subjected to, film body expands, and causes the micropore size on film surface to increase, and porosity improves, and in the high process of interior voltage rise, the diameter of film obviously increases.
Claims (5)
1. hollow-fibre membrane is characterized in that the film forming system mass percent prescription of this hollow-fibre membrane is:
Polyurethane 25～45;
Composite pore-forming 35～60;
Organic low molecular liquid 15～20, each component sum is 100%,
Wherein, described polyurethane is fibre-grade, and the hard section mass ratio with soft section is 1/1～1/5; Described composite pore-forming is the mixture of hole, interface pore-foaming agent and two kinds of materials of hole, non-interface pore-foaming agent, its hole, median surface pore-foaming agent accounts for 10～30% of composite pore-forming gross mass, hole, interface pore-foaming agent is meant and the inconsistent water-insoluble inorganic particulate of described polyurethane, comprises the SiO of average grain diameter 0.01～5 μ m
2And CaCO
3In a kind of mixture of or two kinds of arbitrary proportions; Hole, non-interface pore-foaming agent is meant water-soluble substances, comprises the mixture of water-soluble inorganic particle, water-soluble polymer, water or described water-soluble substances arbitrary proportion; Described water-soluble inorganic particle comprises LiCl, the CaCl of average grain diameter 0.01～5 μ m
2, a kind of among NaCl and the KCl; Described water-soluble polymer comprises polyvinylpyrrolidone or polyethylene glycol; Described organic low molecular liquid is higher boiling, water miscible polyurethane good solvent, comprises the mixture of one or more arbitrary proportions in dimethyl formamide, dimethyl sulfoxide (DMSO) and the dimethylacetylamide.
2. hollow-fibre membrane according to claim 1 is characterized in that the hard section mass ratio with soft section of described polyurethane is 1/2.
3. hollow-fibre membrane according to claim 1 is characterized in that adding the water that is no more than composite pore-forming gross mass 10% in described film forming system formulation.
4. the manufacture method of a hollow-fibre membrane, it is characterized in that this manufacture method adopts following melt-spinning technology: at first according to claim 1,2 or 3 described hollow-fibre membrane mass percent prescriptions require preparation polymer film forming system, be poured into then and heat mandatory premixture in the mixing kettle and close, 130～140 ℃ of heating-up temperatures, back injection double screw extruder is mixed, behind dissolving and melting process, under 130～155 ℃ of temperature, carry out the melt blending spinning membrane system through the hollow spinning pack, after washing operation through the water collection of conventional soln spinning again, promptly obtain described hollow-fibre membrane.
5. the manufacture method of hollow-fibre membrane according to claim 4 is characterized in that behind described melt blending spinning membrane system, and first drawn operation is carried out the water collection again and washed operation; The draw ratio of described stretching process is 3～5 times, and the stretch processing temperature is 40-60 ℃.
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| CN2008100538964A CN101322922B (en) | 2008-07-21 | 2008-07-21 | Hollow fiber film and method for producing the same |
| PCT/CN2009/070717 WO2010009628A1 (en) | 2008-07-21 | 2009-03-10 | A hollow fiber membrane and the preparation thereof |
| HK09104843.2A HK1126708A1 (en) | 2008-07-21 | 2009-05-29 | A kind of hollow fiber membrane and its preparation method |
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| CN2008100538964A CN101322922B (en) | 2008-07-21 | 2008-07-21 | Hollow fiber film and method for producing the same |
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| CN101322922B (en) * | 2008-07-21 | 2011-08-10 | 天津工业大学 | Hollow fiber film and method for producing the same |
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| CN108554204A (en) * | 2018-01-08 | 2018-09-21 | 天津工业大学 | A kind of preparation method of polyvinyl chloride hollow fiber perforated membrane |
| CN114733362B (en) * | 2021-01-07 | 2023-10-31 | 杭州费尔新材料有限公司 | Preparation process of polyolefin hollow fiber membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510181A (en) * | 2002-12-26 | 2004-07-07 | 天津工业大学膜科学与技术研究所 | Built-up membrane additive wet spinning |
| CN1883778A (en) * | 2006-05-26 | 2006-12-27 | 天津工业大学 | Polyurethane blended hollow fiber membrane and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07122162B2 (en) * | 1989-11-29 | 1995-12-25 | 株式会社小松製作所 | Porous hollow fiber and method for producing the same |
| CN101322922B (en) * | 2008-07-21 | 2011-08-10 | 天津工业大学 | Hollow fiber film and method for producing the same |
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2008
- 2008-07-21 CN CN2008100538964A patent/CN101322922B/en not_active Expired - Fee Related
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510181A (en) * | 2002-12-26 | 2004-07-07 | 天津工业大学膜科学与技术研究所 | Built-up membrane additive wet spinning |
| CN1883778A (en) * | 2006-05-26 | 2006-12-27 | 天津工业大学 | Polyurethane blended hollow fiber membrane and method for preparing same |
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| Title |
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| JP平3-174007A 1991.07.29 |
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| CN101322922A (en) | 2008-12-17 |
| WO2010009628A1 (en) | 2010-01-28 |
| HK1126708A1 (en) | 2009-09-11 |
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