CN100361736C - A kind of polyurethane blend hollow fiber membrane and its manufacturing method - Google Patents
A kind of polyurethane blend hollow fiber membrane and its manufacturing method Download PDFInfo
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- CN100361736C CN100361736C CNB2006100138680A CN200610013868A CN100361736C CN 100361736 C CN100361736 C CN 100361736C CN B2006100138680 A CNB2006100138680 A CN B2006100138680A CN 200610013868 A CN200610013868 A CN 200610013868A CN 100361736 C CN100361736 C CN 100361736C
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 54
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
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Abstract
本发明涉及一种聚氨酯共混中空纤维膜及其制造方法。该聚氨酯共混中空纤维膜具有聚合物界面微孔结构，质量百分比配方为：聚氨酯55～75%；分散组分25～45%，其中，聚氨酯硬段与软段的质量比为1/2；分散组分是指聚烯烃类聚合物，包括聚偏氟乙烯和聚丙烯腈。该制造方法按照本发明所述中空纤维膜的质量百分比配方，采用熔体纺丝-拉伸成孔的方法制造，其熔融纺丝温度为170～180℃，喷丝头拉伸倍数为2～4倍，定长热定型温度为50～60℃。所述的中空纤维膜结构致密，支撑性好，并具有较强的分离体系敏感程度和良好的分离记忆功能。所述制造方法不需任何溶剂与添加剂，工艺简单，成本相对较低，对环境无污染，适合现代绿色工业化生产。The invention relates to a polyurethane blended hollow fiber membrane and a manufacturing method thereof. The polyurethane blended hollow fiber membrane has a polymer interface microporous structure, and the mass percentage formula is: polyurethane 55-75%; dispersed components 25-45%, wherein the mass ratio of polyurethane hard segment to soft segment is 1/2; The dispersion component refers to polyolefin polymers, including polyvinylidene fluoride and polyacrylonitrile. According to the mass percentage formula of the hollow fiber membrane of the present invention, the manufacturing method adopts the method of melt spinning-stretching to form holes, the melt spinning temperature is 170-180°C, and the draw ratio of the spinneret is 2-2. 4 times, fixed length heat setting temperature is 50 ~ 60 ℃. The hollow fiber membrane has a dense structure and good support, and has strong separation system sensitivity and good separation memory function. The manufacturing method does not need any solvent and additive, has simple process, relatively low cost, no pollution to the environment, and is suitable for modern green industrialized production.
Description
Technical field
The present invention relates to a kind of hollow-fibre membrane and technology of preparing thereof, be specially a kind of polyurethane comixing hollow-fibre membrane and manufacture method thereof, international Patent classificating number intends being Int.cl.B01D 69/00 (2006.01).
Background technology
Hollow-fibre membrane is as a kind of function parting material with specific form, and its research obtains than much progress with application.Traditional system film forming hole method mainly comprises following several: 1. pore former hole forming method: add suitable solable matter as pore former in casting solution or melt, after the film forming again with its stripping or remove, thereby in film, produce and pore former molecule or the suitable microcellular structure of aggregate size; 2. hole forming method stretches: be used for the film-forming method of bulk polymer moulding such as polyolefin more, after the film forming, make by stretch process that the suitable microstructural defects of generation constitutes microcellular structure in the film; 3. additive thermal decomposition hole forming method: in casting solution or melt, add non-solubility pore-forming material, after film forming, make it resolve into gas and overflow, thereby in film, form corresponding microcellular structure by heat treatment.The film that utilizes said method to make at present, in nature, it all is homogeneous membrane, or perhaps static film, its microcellular structure, as aperture and micro content is metastable, not having the separation memory function (is that microcellular structure is along with the separation system condition, as the variation of pressure and the function that changes), though memory function is perhaps arranged but very weak (be microcellular structure can change but change very little) along with the variation of separation system pressure, do not reach practical level, therefore the film made from said method can not satisfy the membrane process that has memory function to require to separation process.Along with polyblend scientific theory and continuous advancement in technology, that " blend " technology has become is membrane material modified, increase the effective ways of membrane material kind, and the application aspect membrane material is also more and more.
Polyurethane (be polyurethanes, be called for short PU) is a kind of block copolymer, in the big molecule two kinds of segments is arranged, i.e. " soft section " and " hard section ".The former is non-crystallizable under usual conditions, has very low glass transition temperature, is in elastomeric state under the room temperature, can produce very big elongation strain when being subjected to stretching action and have good resilience; Contain the various polarity group among the latter, crosslinked action is played in intermolecular hydrogen bond and crystallization between macromolecular chain, for soft section bigger elongation strain and resilience provide necessary node, can prevent the relative slippage of intermolecular generation.Characteristics such as that PU also has is wear-resisting, chemical-resistant resistance, hydrolysis, molecule can design, shape memory, be a kind of biocompatible polymer material of unique properties, be used widely at aspects such as elastomer, elastomer, foamed plastics, coating and binding agents.The compact structure of PU is strong, and the research and development of its flat sheet membrane at non-pore separation membrane such as gas separation, infiltration evaporation and aspects such as inorganic metal ion separates are subjected to people and pay attention to.But the research of relevant PU hollow-fibre membrane report seldom, and main cause comprises: 1. the vitrification point of PU is low, and self-supporting is poor under the room temperature; The water flux of 2. pure PU film is minimum, no practical value; 3. the shaping of PU hollow-fibre membrane is slower, and the difficulty of making membrane module is bigger.
According to polyblend interface phase separation principle, the inventor once adopted solution shaping (phase inversion) technology, a kind of new diffusion barrier forming hole method has been proposed, promptly utilize polymer/inorganic particle interface phase separation principle to adopt the wet method phase inversion method to prepare and have interface pore characteristics PU/ inorganic particle blended composite film (" a kind of PU/ inorganic particle blended composite film and method for making thereof ", publication number: ZL02131196X.), and adopt the method for solution spinning to prepare polyurethane/SiO with temperature and pressure response performance
2Composite hollow fiber membrane (structure of polyurethane composite hollow fiber membrane and performance X.F.Li, C.F.Xiao, Structure andproperties of Composite Polyurethane Hollow Fiber Membranes, ChineseJ.Polym.Sci., 23 (2005) 203-210).But the compact structure degree of solution shaping PU class hollow-fibre membrane is low, and the part non-reversible deformation in use easily takes place, and makes the accuracy of memory function not ideal enough, uses the back separating property often can not be returned to original state fully.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is a kind of polyurethane comixing hollow-fibre membrane of design and manufacture method thereof.This polyurethane comixing hollow-fibre membrane has the polymer interface microcellular structure, the membrane structure densification, and supportive is good, and has stronger separation system sensitivity and the good memory function of separating; The wet spinning masking technique that the manufacture method of this polyurethane comixing hollow-fibre membrane is more traditional is simple, and has environment friendly, is suitable for suitability for industrialized production and application.
The technical scheme that the present invention solves described polyurethane comixing hollow-fibre membrane technical problem comprises following 5:
(1) a kind of polyurethane comixing hollow-fibre membrane, it has the polymer interface microcellular structure, and the mass percent prescription consists of:
Polyurethane 55～75%;
Dispersed component 25～45%,
Wherein, the mass ratio of segmented polyurethane and soft section is 1/2; Dispersed component is meant Kynoar or polyacrylonitrile.
(2) according to (1) described polyurethane hollow fiber film, described polyurethane comixing hollow-fibre membrane mass percent prescription consists of:
Polyurethane 65～72%;
Dispersed component 28～35%.
(3) a kind of polyurethane comixing hollow-fibre membrane, it has the polymer interface microcellular structure, and is made of polymer and the 3rd component, and wherein, described polymer is made of polyurethane and dispersed component, and the mass ratio of described segmented polyurethane and soft section is 1/2; Dispersed component is meant Kynoar or polyacrylonitrile; Described the 3rd component is inorganic compound calcium carbonate, silica, or simple substance carbon, and its particle diameter is between 0.01～10 μ m; The mass percent prescription of described polyurethane comixing hollow-fibre membrane is: the mass percent that described polyurethane accounts for the polymer total amount is 55～75%; The mass percent that described dispersed component accounts for the polymer total amount is 25～45%; The addition of described the 3rd component is 10～30 quality % of polymer total amount.
(4) according to (3) described polyurethane hollow fiber film, the mass percent that wherein said polyurethane accounts for the polymer total amount is 65～72%; The mass percent that described dispersed component accounts for the polymer total amount is 28～35%.
(5) according to (3) described polyurethane hollow fiber film, the particle diameter of wherein said inorganic particulate is 1 μ m.
The technical scheme that the present invention solves described polyurethane comixing doughnut film manufacturing method technical problem is following (6):
(6) a kind of manufacture method of polyurethane comixing hollow-fibre membrane, it is according to the mass percent prescription of each described polyurethane comixing hollow-fibre membrane in aforementioned (1)-(5), adopt the method for melt spinning-stretching pore-forming to make the polyurethane comixing hollow-fibre membrane, its spinning temperature is 170～180 ℃, the spinneret draft multiple is 2～4 times, and the fixed length heat setting temperature is 50～60 ℃.
Polyurethane comixing hollow-fibre membrane of the present invention is to have utilized polyblend interface phase separation principle and method, wait the polymer interface microcellular structure of controlling blend hollow fiber membrane by suitable selection blend components and proportioning thereof, spinning condition, thereby the polyurethane comixing hollow-fibre membrane of the pore size that can be designed on demand, content and form.Compare with relatively-stationary micro content with the pore size that other blend hollow fiber membrane is single, polyurethane comixing hollow-fibre membrane of the present invention has applicability widely, stronger practicality and better targeted; Polyurethane comixing hollow-fibre membrane particularly of the present invention has adopted two kinds of perhaps not compatible materials of part phase of proper proportion to do decentralized photo and polyurethane comixing film forming, the interface microcellular structure that produces at two kinds of material interfaces has stronger sensitivity to the variation of pressure, realized good separation memory function (being that the interface microcellular structure can correspondingly along with the variation of separating pressure change more sensitively), can satisfy and produce actual or special requirement.Experiment showed, that polyurethane comixing hollow-fibre membrane of the present invention has good pressure-responsive performance, when increasing (for example bringing up to 0.1MPa by 0.05MPa) with separation system pressure, its water flux enlarges markedly and (increases to 597/Lm by 18.15
-2H
-1), and when system pressure reduced (for example being reduced to 0.05MPa by 0.1MPa), its water flux recovered initial value and (is reduced to 18.5/Lm by 597
-2H
-1), shown accurate pressure response (referring to embodiment 3).Polyurethane comixing doughnut film manufacturing method of the present invention is a matrix phase with described polyurethane, with described dispersed component is decentralized photo, as the blend extrusion equipment, the method manufacturing of employing melt spinning-stretching pore-forming has the polyurethane comixing hollow-fibre membrane of polymer interface microcellular structure with double screw extruder.Owing to adopted the method for melt spinning-stretching pore-forming, compared with prior art, do not need any solvent and additive in the film-forming method process, so manufacture method is simple, cost is relatively low, and particularly environmentally safe is fit to modern green industrialized production.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment, but the present invention is not subjected to the restriction of embodiment:
The mass percent prescription of polyurethane comixing hollow-fibre membrane of the present invention (hereinafter to be referred as hollow-fibre membrane or film) is:
Polyurethane 55～75%;
Dispersed component 25～45%,
Wherein, the mass ratio of segmented polyurethane and soft section is 1/2; Dispersed component be meant with polyurethane be that non-thermodynamic compatibility or part are compatible, molten limit is approaching with polyurethane, perhaps decomposition temperature is higher than the polyurethane processing temperature and softening point is lower than or near the molten limit of polyurethane, and the polymer that final gained polyurethane comixing hollow-fibre membrane is not had physics damage or chemical damage, usually select polyolefin polymers for use, comprise Kynoar and polyacrylonitrile.
The basal lamina material of hollow-fibre membrane of the present invention or matrix phase are polyurethane.Its chemical constitution comprises soft section and hard section.Hard section is the aromatic diisocyanate that micromolecular dihydroxylic alcohols or diamine connect; Soft section can be polyether Glycols or polyester diol.Studies show that, the mass ratio of segmented polyurethane and soft section be 1/2 o'clock more satisfactory, but the mass ratio of segmented polyurethane and soft section can be selected in 1/1～1/10 scope.Except that hard section with soft section mass ratio, all other physical and chemical index of polyurethane should reach the fibre-grade level.
The dispersed component of described hollow-fibre membrane or the choose reasonable of decentralized photo are the key problem in technology of hollow-fibre membrane of the present invention.It is selected according to being: be that non-thermodynamic compatibility or part are compatible with matrix phase 1.; 2. can carry out melt spinning with polyurethane comixing, promptly its molten limit and polyurethane near or its decomposition temperature be higher than the processing temperature of polyurethane and softening point is lower than or near the molten limit of polyurethane; 3. final gained hollow-fibre membrane there are not physics damage or chemical damage.The embodiment of dispersed component of the present invention has selected and the perhaps inconsistent mutually material of polyurethane part, mainly comprises the synthesis of polyolefins base polymer, comprises Kynoar and polyacrylonitrile etc.Experimental study shows, in the prescription of the present invention, within the specific limits, increase with dispersed component content, the water flux of gained blend hollow fiber membrane increases, but the corresponding decline of amplitude of its temperature, pressure response, therefore, it is 28～35% more satisfactory that the content of dispersed component should be controlled at, although its proportioning can reach 25～45%.
For further increasing the water flux of film, perhaps for satisfying specific purposes requirement, further feature of the present invention is to add the 3rd component in the process of co-blended spinning simultaneously, also promptly adds the 3rd component in described prescription.The 3rd component is an inorganic particulate.The selection of described the 3rd component inorganic particulate is according to being: 1. inorganic particulate should have certain particle, and can be evenly dispersed among matrix phase or the basal lamina material, and its granularity requirements is 0.01-10 μ m, but more satisfactory be about 1 μ m; 2. after inorganic particulate added, the polyurethane/inorganic particle blended thing of gained should have good fiber or film forming and processing characteristics, add inorganic particulate in other words after, should not reduce the film forming and the processing characteristics thereof of original copolymer; 3. the hollow-fibre membrane to final molding does not have physics damage and chemical damage.The 3rd component that the present invention selects for use can be an inorganic compound, as calcium carbonate (CaCO
3) and silica (SiO
2) etc., also can be simple substance, as carbon (C) etc.The addition of inorganic particulate is in 10～30% scopes of polymer total amount (being the gross mass of polyurethane and dispersed component polymer blend), otherwise will cause that gained film withstand voltage properties descends to some extent.After adding the 3rd component, the mass percent prescription of described hollow-fibre membrane can correspondingly reduce the ratio of polymer total amount.
Need explanation to be, although can add the water flux that inorganic particulate increases the gained film in the prescription of the present invention, it is nonessential.The present invention can not add any other component fully in film-forming process, can solve technical problem to be solved by this invention.This is one of main distinction of the present invention and prior art, and also therefore, forming hole method of the present invention can be described as the polymer interface hole forming method.
The key technology of polyurethane comixing doughnut film manufacturing method of the present invention is to adopt the process of melt spinning-stretching pore-forming.The key of this method is to select suitable spinning condition, comprises spinning temperature, and draw ratio etc. are so that be met the hollow-fibre membrane that instructions for use has the interface microcellular structure.With regard to spinning temperature, the melt processing temperature of polyurethane is relatively low, usually about 160 ℃.Test shows, the decentralized photo of selecting for use by principle of the present invention with the process of the common plasticizing of polyurethane in melt processing temperature have bigger reduction.For example, the processing temperature of Kynoar is usually more than 200 ℃, when the present invention adopts twin-screw to carry out co-blended spinning as the mass percent prescription by polyurethane 75%, Kynoar 25%, Qi Ge district temperature is controlled at about 170 ℃, can reach spinning effect (referring to embodiment 1) preferably.Discover, behind principle selection decentralized photo of the present invention, the best scope of the twin-screw spinning temperature of gained polyurethane blends is 170～180 ℃, and the selection of concrete technological temperature is relevant with the quality percentage composition of decentralized photo, the content height of decentralized photo, spinning temperature just should be high.
Pore-forming mechanism of the present invention is to utilize the difference of polymer thermodynamic compatibility to obtain the interface micropore, so further feature of the present invention is to select suitable spinneret draft ratio, to promote the formation of interface microcellular structure between the two-phase, make the separation degree increase at the interface of decentralized photo and matrix phase, thereby improve the porosity of film and change its microcellular structure.More satisfactory stretching ratio should be controlled in 2～4 times of scopes.Stretching ratio is low excessively, and drawing effect is not obvious, and the porosity of gained film is lower, does not possess use value; Draw ratio is too high, then can make film itself produce bigger defective even breaks, and runs counter to desire.After the stretching, also will fixed length thermal finalization under 50～60 ℃ of temperature, relatively stable until fibre structure.Doughnut film manufacturing method of the present invention is compared with traditional solution spinning process, has that technology is simple, cost is low, pollution-free, environmental friendliness, is easy to characteristics such as industrializing implementation.
The polyurethane comixing hollow-fibre membrane that foundation prescription of the present invention and manufacture method can obtain having polymer interface microcellular structure feature.It has overcome that traditional solution spinning process obtains that hollow fiber film structure is comparatively loose, supportive is relatively poor and is insensitive in the pressure-responsive process, can not return to the shortcoming of original state fully.Studies show that, the interface microcellular structure of this hollow-fibre membrane, comprise pore size and micro content etc., depend on compatibility, thermal property, relative amount and the stretching condition etc. of polyurethane substrates and dispersed component.If the compatibility of decentralized photo and matrix phase is good, then the degree that is separated at two-phase interface place is little in the hollow-fibre membrane, and the interface pore size is little, and porosity is low.Interface microcellular structure characteristics are not remarkable; If the compatibility of two phase components is poor, then the degree that is separated at two-phase interface place is big, and the interface pore size is big, the porosity height, and interface microcellular structure characteristics are remarkable; If the mechanical property difference of two phase components, then when system pressure changed, the deformation degree difference of two-phase also caused interface microcellular structure respective change; When system is replied initial state, because matrix phase polyurethane has good shape memory characteristic,, be tending towards being returned to initial state so interface pore size, content and the form of hollow-fibre membrane also respective change can take place, show good memory characteristic.Certainly, under the constant situation of other condition, in the process of melt spinning, increase spinneret draft and be separated between the polymer blend than promoting, thus the micropore size of raising gained hollow-fibre membrane.These achievements in research help the hollow-fibre membrane that adopts method of the present invention to have required interface microcellular structure feature by the manufacturing of film product requirement and possess accurate pressure response performance and high performance-price ratio.
Provide specific embodiments of the invention below:
Embodiment 1:
With fibre-grade polyurethane (hard section/soft section mass ratio is 1/2) is matrix phase, with the Kynoar is dispersed component, by Kynoar content is 25% (mass percent, down together), polyurethane content is after 75% proportioning is evenly mixed polyurethane and Kynoar section, add double screw extruder and carry out the melt blending spinning, spinning temperature all is controlled at 170 ℃, control spinneret draft ratio is respectively 2,2.5,3,4 times under the room temperature, relatively stable 60 ℃ of following fixed length thermal finalizations again to fibre structure, can obtain having the hollow-fibre membrane of different microcellular structures.
Embodiment 2:
Press embodiment 1 method, four kinds of spinneret drafts are measured its water flux than resulting hollow-fibre membrane under 0.1MPa pressure and 20 ℃ of temperature, resulting analog value is respectively 71,107,123,189 (Lm
-2H
-1), show the draw ratio of the inventive method and the proportional relation of water flux.
Embodiment 3:
Press embodiment 1 method, is the spinneret draft ratio 4 resulting hollow-fibre membranes, 20 ℃ of temperature, and 0.05,0.1,0.15,0.1, in the cyclic process of 0.05Mpa pressure, measure its water flux respectively, resulting analog value is respectively 18.15,189,597,188,18.5 (Lm
-2H
-1), show the good pressure-responsive feature of film of the present invention.
Embodiment 4:
With fibre-grade polyurethane (hard section/soft section mass ratio is 1/2) is matrix phase, with the Kynoar is dispersed component, by Kynoar content is 25%, 30%, after 45% proportioning (all the other are polyurethane) is mixed polyurethane and Kynoar section, add in the double screw extruder and carry out the melt blending spinning, spinning temperature is controlled at 170 ℃ respectively, about 175 ℃ and 180 ℃, resulting hollow-fibre membrane strand quality is better, control spinneret draft ratio is 2 times under the room temperature, relatively stable 60 ℃ of following fixed length thermal finalizations again to fibre structure, can obtain described hollow-fibre membrane.
Above-mentioned three kinds of films are at 0.1MPa, under 20 ℃, measure its water flux, and the analog value that obtains is respectively 71,153,189 (Lm
-2H
-1), it is proportional to show decentralized photo Kynoar content and water flux, but that Kynoar content is 45% doughnut film-strength is relatively low, illustrates that the proportioning of decentralized photo should not surpass 45%.
Embodiment 5:
With fibre-grade polyurethane (hard section/soft section mass ratio is 1/2) is matrix phase, with the Kynoar is dispersed component, by Kynoar content is 25%, polyurethane content is 75% proportioning mixing polyurethane and Kynoar section, and sneaking into the average grain diameter that accounts for total polymer mass 30% again is the CaCO of 1 μ m
3Behind the micro mist, add in the double screw extruder and carry out the melt blending spinning, each is distinguished spinning temperature and all is controlled at about 173 ℃, at room temperature controlling the spinneret draft ratio is 2,2.5,3,4 times, relatively stable through 55 ℃ of fixed length thermal finalizations again to fibre structure, can obtain having the hollow-fibre membrane of different microcellular structures.
Embodiment 6:
Press the method for embodiment 5, four kinds of spinneret drafts are measured its water flux than resulting hollow-fibre membrane under 0.1MPa pressure and 20 ℃ of temperature, resultant analog value is respectively 140,210,245.4,389 (Lm
-2H
-1).The same with embodiment 2, equally also show the draw ratio of the inventive method and the proportional relation of water flux, but water flux is multiplied.
Embodiment 7:
Press the method for embodiment 5, is the spinneret draft ratio 4 resulting hollow-fibre membranes, 20 ℃ of temperature, 0.05,0.1,0.15,0.1, in the cyclic process of 0.05Mpa pressure, measure its water flux respectively, resulting analog value is respectively 38.27,389.79,1158.75,390,38.50 (Lm
-2H
-1), equally also show the good pressure-responsive feature of film of the present invention.Compare with embodiment 3, water flux is multiplied.
Embodiment 8:
Press prescription and the method for embodiment 5, only change CaCO
3Content be 15%, the spinneret draft that obtains is than the hollow-fibre membrane that is 4,20 ℃ of temperature, and 0.05,0.1,0.15,0.1, in the cyclic process of 0.05Mpa, measure its water flux respectively, resultant analog value is respectively 25,225,783,225,25 (Lm
-2H
-1), illustrate that the 3rd constituent content and water flux are also proportional, and influence is responsive.
Embodiment 9:
Press the method for embodiment 5, with described inorganic particulate by CaCO
3Change the close SiO of granularity into
2Or C, the described hollow-fibre membrane that makes under the constant situation of other condition, under same test process and condition, resulting water flux data and CaCO
3Corresponding data basically identical.
Embodiment 10:
Press the method for embodiment 1, the dispersed component polymer is adjusted into polyacrylonitrile, its content is controlled at 25% of total polymer mass, spinning temperature is 160 ℃, control spinneret draft ratio is 2.5 times under the room temperature, relatively stable through fixed length thermal finalization under 50 ℃ of temperature again to fibre structure, can obtain described hollow-fibre membrane.With the described hollow-fibre membrane of gained 20 ℃ of temperature, 0.05,0.1,0.15,0.1, in the cyclic process under the 0.05Mpa pressure, measure its water flux respectively, the analog value that obtains is respectively 20,31,43,31,20 (Lm
-2H
-1), rule is with embodiment 3, but the sensitivity deficiency that water flux changes.
Claims (6)
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| CN101306329B (en) * | 2007-05-17 | 2010-12-01 | 深圳市龙澄高科技环保有限公司 | Preparation method of polyurethane hollow fiber filter membrane |
| CN101322922B (en) * | 2008-07-21 | 2011-08-10 | 天津工业大学 | Hollow fiber film and method for producing the same |
| CN102080277B (en) * | 2010-12-09 | 2013-09-04 | 武汉纺织大学 | Compound elastic fiber and preparation method thereof |
| CN102295323B (en) * | 2011-06-16 | 2013-06-05 | 天津工业大学 | Water processing method |
| CN102728249B (en) * | 2012-07-22 | 2014-07-23 | 天津工业大学 | Polymer hollow fiber porous membrane and preparation method thereof |
| CN115991017B (en) * | 2022-11-28 | 2024-07-19 | 苏州大学 | Double-layer heat-sensitive fireproof flame-retardant nonwoven material and preparation method thereof |
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