CN103041717A - Yarn fiber reinforced double-layer tubular filtering membrane and method for preparing same - Google Patents
Yarn fiber reinforced double-layer tubular filtering membrane and method for preparing same Download PDFInfo
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- CN103041717A CN103041717A CN2013100128829A CN201310012882A CN103041717A CN 103041717 A CN103041717 A CN 103041717A CN 2013100128829 A CN2013100128829 A CN 2013100128829A CN 201310012882 A CN201310012882 A CN 201310012882A CN 103041717 A CN103041717 A CN 103041717A
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Abstract
The invention discloses a yarn fiber reinforced double-layer tubular filtering membrane. The tubular filtering membrane has a double-layer structure, wherein the inner layer is a first polymer membrane, while the outer layer is a second polymer membrane; and yarn fibers distributed in parallel are arranged in the inner layer or the outer layer for mechanically reinforcing the tubular filtering membrane. The tubular filtering membrane provided by the invention is obviously improved in transverse compression resistance and blast resistance as well as membrane safety while having excellent axial mechanical properties; and the tubular filtering membrane with excellent overall performance for external-compression type filtering or internal-compression type filtering by adjusting the distribution positions of the yarn fibers and the double-layer structure and the properties of the membrane. The invention also discloses a method for preparing the tubular filtering membrane; and the two-layer synchronous coextrusion technique is employed, so that the production efficiency of the membrane can be effectively improved and the preparation cost of the tubular filtering membrane can be reduced.
Description
Technical field
The invention belongs to the membrane technology field, particularly the fine tubular type filter membrane and preparation method thereof that strengthens of a kind of double-deck yarn.
Background technology
The film separation process is take the selective film that sees through as separating medium, under the promotion of external force, and a kind of new and effective isolation technics that mixture is separated, purifies, concentrates.And the tubular filter film has widely application because its effective separation area is large, the characteristics such as modular construction is simple, operation easy to operate in fields such as water treatment, biological medicine, food chemistries.Yet than inoranic membranes such as pottery, metals, the mechanical strength of macromolecule tubular type filter membrane is relatively relatively poor, use and cleaning process in easily have fracture of wire, the problem such as flatten, break.In order to improve the mechanical property of tubular filter film, fiber and braided tube thereof are widely used in the manufacturing of filter membrane.
Fiber braided tube is applied in the preparation of tubular filter film, often adopts the outer technology that applies casting solution of braided tube, so that filter membrane has good stretch-proof and compressive property.Patent US 4061821 and US 5472607 disclose respectively a kind of method that internal layer is PAN hollow-fibre membrane and the PVDF hollow-fibre membrane of braided tube for preparing, and the mechanical property of film is significantly increased.In addition, in the preparation of enhancement mode tubular membrane, see also that outside braided tube applying double-deck casting solution (CN 102160967A), fibrage and casting solution applies technologies of preparing such as carrying out synchronously all having inside and outside (CN 101543731A), the braided tube polymeric membrane for separation layer (CN 1864828A).But often there is following problem in the tubular membrane that adopts braided tube to strengthen: adhesive property is relatively poor between braided tube and polymeric membrane, exist in the use procedure come off, peeling; The braided tube of conventional method preparation strengthens tubular membrane, generally is only applicable to external-compression type and filters; Be subjected to the impact of existing fibrage efficient and cost, this tubular membrane cost is relatively high.
In addition, the fiber without braiding also can be directly used in raising tubular type film strength.Patent WO 03/097221 proposes fiber and casting solution are introduced spinning head simultaneously, thereby prepares the fiber-reinforced composite film with the similar inside/outside layer of homogeneous hollow-fibre membrane structure.But, above-mentioned fiber reinforced film since fiber only axial distribution therefore in film, only improved the stretch-proof performance of film on axially, resistance to compression and anti-burst performance do not have clear improvement; Simultaneously, inevitably there are certain adhesion problem in fiber and film liquid, and there is certain potential safety hazard in the film silk in long-term use procedure.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of high flux, mechanics, withstand voltage, hold back and the excellent combination property such as antipollution, applicable to the fine double-tube type filter membrane that strengthens of the yarn that external-compression type filters or inner pressed filters.Tubular filter film of the present invention is double-decker, and internal layer is the first polymer film, and skin is the second polymer film, and internal layer and/or the outer fine mechanics enhancing that is used for described tubular filter film of yarn that contains parallel distribution.The adjustment of the distributing position of the double-decker by film and performance, yarn fibre makes this tubular filter film possess high flux, in the time of Good All-around Property, also makes this film have widely applicability in different applications.
The technical solution used in the present invention is as follows:
The fine double-tube type filter membrane that strengthens of a kind of yarn, it is characterized in that: described tubular filter film is double-decker, internal layer is the first polymer film, skin is the second polymer film, and described tubular filter film is distributed with for the yarn that strengthens fine, the external diameter of described tubular filter film is 0.8～5.0mm, and internal diameter is 0.4～3.0mm.
Wherein,
The polymeric material of described the first polymer film and the second polymer film is similar polymers or non-similar polymers; Similar polymers of the present invention comprises the similar polymers of all size that the physical parameters such as molecular weight, molecular weight distribution are different.
As preferably, described polymeric material is selected from any one in Kynoar, polyvinyl chloride, polyether sulfone, polysulfones, polyacrylonitrile, the cellulose acetate; For example, the polymeric material of the first polymer film can be selected Kynoar, and the polymeric material of the second polymer film can be selected the Kynoar of other different specifications of the physical parameters such as molecular weight, molecular weight distribution; Also can be that the polymeric material of the first polymer film and the second polymer film is all selected the identical Kynoar of physical parameter such as molecular weight, molecular weight distribution.
As preferably, described yarn fibre can only be distributed in the first polymer film (Fig. 1-1), or only is distributed in the second polymer film (Fig. 1-2), or all has the yarn fibre to be distributed in the first polymer film and in the second polymer film (Fig. 1-3).
More preferably, described yarn fibre be symmetrically distributed in the first polymer film or the second polymer film in.
More preferably, the fine quantity of described yarn is 3～12.
As preferably, any one or the mixed yarn more than two kinds that described yarn fiber material is selected from cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber, the glass fibre are fine, are distributed in the first polymer film or the yarn fibre in the second polymer film can be identical or different; Described yarn refers to short fiber is elongated the yarn of the length that forms after the twisting, and short fiber material is not mixed yarn simultaneously, is pure yarn when short fiber material is identical; Described fibre refers to be closed up by many long fibres the silk thread of the rear length that forms, and long fiber material is not fine for blending simultaneously, is pure fibre when long fiber material is identical.Yarn of the present invention is fine, comprises yarn and fibre, specifically comprises mixed yarn, pure yarn, blending fibre, pure fibre; Described pure yarn fibre (comprises cellulose yarn including but not limited to pure cellulose yarn is fine, cellulose fiber), polyester yarn is fine (to comprise polyester yarn, polyester is fine), polyamide yarn is fine (to comprise polyamide yarn, polyamide is fine), the polyvinyl alcohol yarn is fine (to comprise the polyvinyl alcohol yarn, polyvinyl alcohol is fine), polypropylene yarn is fine (to comprise polypropylene yarn, polypropylene is fine), the polyacrylonitrile yarn is fine (to comprise the polyacrylonitrile yarn, polyacrylonitrile is fine), the polyvinyl chloride yarn is fine (to comprise the polyvinyl chloride yarn, polyvinyl chloride is fine), carbon fiber yarn is fine (to comprise carbon fiber yarn, carbon fiber is fine), glass fiber yarn is fine (to comprise glass fiber yarn, glass fibre is fine) etc.; Described mixed yarn fibre including but not limited to polyester cotton blended yarn fine (polyester and cellulose blending), bright and beautiful silk/cotton blended yarn fine (polyamide and cellulose blending), wash nitrile mixed yarn fine (polyester and polyacrylonitrile blending) etc.
Tubular filter film of the present invention is double-decker, is distributed with the yarn fibre in the film, and the yarn fibre has ensured the hot strength that film is axial, double-decker make the horizontal resistance to compression of film and anti-burst performance and film security be improved significantly.And by distributing position, the double-decker of film and the adjustment of performance of yarn fibre, can obtain the tubular filter film of the excellent combination property of suitable external-compression type filtration or inner pressed filtration.Wherein, when being distributed with in the first polymer film when fine for the yarn that strengthens, the first polymer film mainly plays supporting layer, and the second polymer film exodermis is than compact texture, mainly play functional layer (Fig. 1-1), this tubular filter film is applicable to the external-compression type filtration system; When being distributed with in the second polymer film when fine for the yarn that strengthens, the second polymer film mainly plays supporting layer, the first polymer film endodermis is than compact texture, mainly plays functional layer (Fig. 1-2), and this tubular filter film is applicable to the inner pressed filtration system; When being distributed with in the first polymer film and in the second polymer film when fine for the yarn that strengthens, the first polymer film endodermis the second polymer film exodermis is than compact texture, make the two layers of polymers film all have good intensity and separating effect (Fig. 1-3), this tubular filter film both had been applicable to the external-compression type filtration system, also was applicable to the inner pressed filtration system.
Second purpose of the present invention provides the application of described yarn fine enhancing double-tube type filter membrane in external-compression type filtration system or inner pressed filtration system, and described external-compression type filtration and inner pressed filtration system are including but not limited to medical industry (traditional Chinese drug inspissation, pesticide producing, bio-fermented liquid filtration etc.), food industry (fructose separation and purification, food additives are concentrated, dairy products are produced, making with extra care of wine, natural colouring matter extraction etc.), dye chemical industry and auxiliary agent, biotechnology (albumen, the clarification of polypeptide etc. and refining), environmental protection and water treatment field (Industrial Wastewater Treatment and the reuse such as spinning printing and dyeing, the processing of municipal wastewater, the preparation of all kinds of water that industry and life are required etc.).
The 3rd purpose of the present invention provides the fine preparation method who strengthens the double-tube type filter membrane of a kind of yarn, adopts double-deck synchronously coextrusion technology, realizes the one-step method film forming, and the preparation method may further comprise the steps:
(1) casting solution of preparation the first polymer film and the second polymer film, the deaeration set aside for use;
(2) casting solution of the first polymer film and the second polymer film is injected respectively the casting solution runner of the first polymer film of spinning head and the casting solution runner of the second polymer film, the yarn fibre that is used for strengthening is arranged in parallel and passes in the casting solution runner, under the acting in conjunction of core liquid and coagulating bath, by the solution phase conversion method, the fine double-tube type filter membrane that strengthens of double-deck synchronously coextrusion resultant yarn; Described spinning head is three flow passage structures, from inside to outside is followed successively by the casting solution runner (B) of core liquid runner (A), the first polymer film, the casting solution runner (C) of the second polymer film;
(3) with the double-tube type filter membrane of coextrusion through rolling, clean, dry after, obtain the fine double-tube type filter membrane that strengthens of yarn of structure and stable performance.
Wherein, the casting solution of the first polymer film and the second polymer film all comprises polymeric material, modifier, pore former, several components of solvent.Can according to actual needs, adjust prescription and the preparation condition of casting solution.The prescription of two kinds of casting solutions and preparation condition can be identical or different, namely the polymeric material of two kinds of casting solutions, modifier, pore former, solvent can be material of the same race or material not of the same race, the content of every kind of material also can be identical or different, wherein, material of the same race can comprise the material of the same race of all size that the physical parameters such as molecular weight, molecular weight distribution are different.Simultaneously, the batching of two kinds of casting solutions and dwell temperature also can be identical or different.
As preferably, described polymeric material is selected from any one of Kynoar, polyvinyl chloride, polyether sulfone, polysulfones, polyacrylonitrile, cellulose acetate, and its quality percentage composition is 8～30%; It is 1 * 10 that modifier is selected from molecular weight
4～1 * 10
6In PVP, silica, titanium oxide, the aluminium oxide any one or multiple, its quality percentage composition is 0.5～6%; Pore former be selected from water, ethanol, glycerine, ethylene glycol, molecular weight be in 400～1000 the polyethylene glycol any one or multiple, its quality percentage composition is 0.5～8%; Solvent is selected from any one in DMF, DMA, 1-METHYLPYRROLIDONE, the dimethyl sulfoxide (DMSO), and its quality percentage composition is 56～91%; The preparation of casting solution and dwell temperature are 60～90 ℃.For example, it is 400 polyethylene glycol that the pore former of the first polymer film can be selected molecular weight, and it is 1000 polyethylene glycol that the pore former of the second polymer film can be selected molecular weight; Also can be that it is 400 polyethylene glycol that the pore former of the first polymer film and the second polymer film is all selected molecular weight.
Wherein, the casting solution runner of the casting solution runner of core liquid runner, the first polymer film, the second polymer film can take different shapes; The casting solution of the casting solution of core liquid, the first polymer film, the second polymer film injects spinning head can adopt different order, but finally reaches the effect of synchronous coextrusion.
As preferably, core liquid runner is circular flow channel, and the casting solution runner of the casting solution of the first polymer film, the second polymer film is annular channel.
As preferably, can inject first core liquid, inject simultaneously again the casting solution of the first polymer film and the casting solution of the second polymer film; Or inject simultaneously the casting solution of core liquid, the first polymer film and the casting solution of the second polymer film.
As preferably, described yarn fibre only passes the casting solution runner (Fig. 2-1) of the first polymer film or only passes the casting solution runner (Fig. 2-2) of the second polymer film, or all has the yarn fibre to pass the casting solution runner of the first polymer film and the casting solution runner of the second polymer film (Fig. 2-3); Described passing refers to the yarn fibre is penetrated in the runner of spinning head, and is fixed in film silk gathering-device along spinning threadling.By such mode, can make described yarn fibre only be distributed in first polymer film interior (Fig. 1-1) of double-tube type filter membrane, or only be distributed in the second polymer film of double-tube type filter membrane (Fig. 1-2), or all there is the yarn fibre to be distributed in the first polymer film of double-tube type filter membrane and in the second polymer film (Fig. 1-3).
More preferably, described yarn fibre be symmetrically distributed in the first polymer film or the second polymer film in;
More preferably, the fine quantity of described yarn is 3～12.
As preferably, any one or the mixed yarn more than two kinds that described yarn fiber material is selected from cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber, the glass fibre are fine, are distributed in the first polymer film or the yarn fibre in the second polymer film can be identical or different; Described yarn refers to short fiber is elongated the yarn of the length that forms after the twisting, and short fiber material is not mixed yarn simultaneously, is pure yarn when short fiber material is identical; Described fibre refers to be closed up by many long fibres the silk thread of the rear length that forms, and long fiber material is not fine for blending simultaneously, is pure fibre when long fiber material is identical.Yarn of the present invention is fine, comprises yarn and fibre, specifically comprises mixed yarn, pure yarn, blending fibre, pure fibre.Described pure yarn fibre (comprises cellulose yarn including but not limited to pure cellulose yarn is fine, cellulose fiber), polyester yarn is fine (to comprise polyester yarn, polyester is fine), polyamide yarn is fine (to comprise polyamide yarn, polyamide is fine), the polyvinyl alcohol yarn is fine (to comprise the polyvinyl alcohol yarn, polyvinyl alcohol is fine), polypropylene yarn is fine (to comprise polypropylene yarn, polypropylene is fine), the polyacrylonitrile yarn is fine (to comprise the polyacrylonitrile yarn, polyacrylonitrile is fine), the polyvinyl chloride yarn is fine (to comprise the polyvinyl chloride yarn, polyvinyl chloride is fine), carbon fiber yarn is fine (to comprise carbon fiber yarn, carbon fiber is fine), glass fiber yarn is fine (to comprise glass fiber yarn, glass fibre is fine) etc.; Described mixed yarn fibre including but not limited to polyester cotton blended yarn fine (cellulose and polyester blended), bright and beautiful silk/cotton blended yarn fine (polyamide and cellulose blending), wash nitrile mixed yarn fine (polyester and polyacrylonitrile blending) etc.
Described core liquid is water or water/solvent liquid, and temperature is 20～60 ℃, and solvent is any one in DMF, DMA, 1-METHYLPYRROLIDONE, the dimethyl sulfoxide (DMSO) in the mixed liquor, and its quality percentage composition is 5～30%; Described solidification liquid is water or water/solvent liquid, temperature is 20～60 ℃, and solvent is DMF, N in the mixed liquor, in N-dimethylacetylamide, 1-METHYLPYRROLIDONE, the dimethyl sulfoxide (DMSO) any one, its quality percentage composition is 5～30%.
Among the preparation method of the fine enhancing of this yarn double-tube type filter membrane, the fine casting solution with the first polymer film and the second polymer film of yarn is finally extruded from spinning head synchronously, the coil stripping speed that is the discharging speed of casting solution and yarn fibre is consistent, it is 5～30 m/mins, realized continuous one-step method film forming, thereby effectively improved the production efficiency of film, reduced preparation cost.
Beneficial effect of the present invention is:
(1) adopt the fine mechanical property that improves film of yarn, with avoid or reduce the tubular filter film use and cleaning process in the fracture of wire phenomenon.
(2) the tubular filter film is double-decker, so that the yarn fibre is when ensureing the film axial tensile strength, double-decker makes the horizontal resistance to compression of film and anti-burst performance, and the security performance of film be improved significantly.
(3) adjustment by the fine quantity of yarn and distributing position, the control of formula of casting and membrance casting condition can be prepared the tubular filter film of different structure and performance, filters or the inner pressed filtration system to be applicable to external-compression type.
(4) the fine double-tube type filter membrane that strengthens of yarn of the present invention has high flux, excellent holds back, the performance such as hydrophilic and antipollution.
(5) the present invention will directly apply to without the yarn fibre of braiding the mechanical property that improves film, and the technology that adopts yarn fibre and the synchronous coextrusion of double-deck casting solution, can effectively improve the production efficiency of film, reduce preparation cost.
Description of drawings
Fig. 1 is the fine section structure schematic diagram that strengthens the double-tube type filter membrane of yarn of the present invention:
Wherein, Fig. 1-1 expression yarn fibre only is distributed in the double-tube type filter membrane in the first polymer film, Fig. 1-2 represents that the yarn fibre only is distributed in the double-tube type filter membrane in the second polymer film, and Fig. 1-3 expression all has the yarn fibre to be distributed in the first polymer film and the double-tube type filter membrane in the second polymer film;
Among the figure, 1 is the first polymer film, and 2 is the second polymer film, and 3 is that yarn is fine.
Fig. 2 is the profile of spinning head discharging opening of the present invention:
Wherein, Fig. 2-1 expression yarn fibre only passes the casting solution runner of spinning head the first polymer film, Fig. 2-2 expression yarn fibre only passes the casting solution runner of spinning head the second polymer film, and Fig. 2-3 expression all has the yarn fibre to pass the casting solution runner of spinning head the first polymer film and the casting solution runner of the second polymer film;
Among the figure, A is that core liquid runner, B are the casting solution runner of the first polymer film, the casting solution runner that C is the second polymer film, and 3 is that yarn is fine.
The specific embodiment
Describe the present invention in detail below in conjunction with drawings and Examples.
Yarn of the present invention is fine to strengthen double-tube type filter membrane section structure schematic diagram as shown in Figure 1.This tubular filter film is double-decker, and internal layer is the first polymer film, and skin is the second polymer film, and this tubular filter film is distributed with for the yarn that strengthens finely, and the external diameter of described tubular filter film is 0.8～5.0mm, and internal diameter is 0.4～3.0mm.Difference according to the fine embedded position of yarn, this tubular filter film has 3 kinds of structures, be that the yarn fibre only is distributed in the first polymer film (Fig. 1-1), the yarn fibre only is distributed in the second polymer film (Fig. 1-2), all has the yarn fibre to be distributed in the first polymer film and the second polymer film interior (Fig. 1-3).
Wherein, the polymeric material of described the first polymer film and the second polymer film is similar polymers or non-similar polymers.
As preferably, described polymeric material is selected from any one in Kynoar (PVDF), polyvinyl chloride (PVC), polyether sulfone (PES), polysulfones (PSF), polyacrylonitrile (PAN), the cellulose acetate (CA);
As preferably, described yarn fibre is symmetrically distributed in the first polymer film or in the second polymer film.
More preferably, the fine quantity of described yarn is 3～12.
As preferably, any one or the mixed yarn more than two kinds that described yarn fiber material is selected from cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber, the glass fibre are fine, are distributed in the first polymer film or the yarn fibre in the second polymer film can be identical or different; Described yarn refers to short fiber is elongated the yarn of the length that forms after the twisting, and short fiber material is not mixed yarn simultaneously, is pure yarn when short fiber material is identical; Described fibre refers to be closed up by many long fibres the silk thread of the rear length that forms, and long fiber material is not fine for blending simultaneously, is pure fibre when long fiber material is identical.Yarn of the present invention is fine, comprises yarn and fibre, specifically comprises mixed yarn, pure yarn, blending fibre, pure fibre.Described pure yarn fibre (comprises cellulose yarn including but not limited to pure cellulose yarn is fine, cellulose fiber), polyester yarn is fine (to comprise polyester yarn, polyester is fine), polyamide yarn is fine (to comprise polyamide yarn, polyamide is fine), the polyvinyl alcohol yarn is fine (to comprise the polyvinyl alcohol yarn, polyvinyl alcohol is fine), polypropylene yarn is fine (to comprise polypropylene yarn, polypropylene is fine), the polyacrylonitrile yarn is fine (to comprise the polyacrylonitrile yarn, polyacrylonitrile is fine), the polyvinyl chloride yarn is fine (to comprise the polyvinyl chloride yarn, polyvinyl chloride is fine), carbon fiber yarn is fine (to comprise carbon fiber yarn, carbon fiber is fine), glass fiber yarn is fine (to comprise glass fiber yarn, glass fibre is fine) etc.; Described mixed yarn fibre including but not limited to polyester cotton blended yarn fine (cellulose and polyester blended), bright and beautiful silk/cotton blended yarn fine (polyamide and cellulose blending), wash nitrile mixed yarn fine (polyester and polyacrylonitrile blending) etc.
The specific embodiment that the present invention prepares the fine enhancing of yarn double-tube type filter membrane is as follows:
(1) casting solution of preparation the first polymer film and the second polymer film: with polymeric material, modifier, pore former and solvent blend, deaeration set aside for use.
Wherein, the prescription of two kinds of casting solutions and preparation condition can be identical or different.As preferably, polymeric material is selected from any one in Kynoar (PVDF), polyvinyl chloride (PVC), polyether sulfone (PES), polysulfones (PSF), polyacrylonitrile (PAN), the cellulose acetate (CA), and its quality percentage composition is 8～30%; It is 1 * 10 that modifier is selected from molecular weight
4～1 * 10
6PVP (PVP), silica (SiO
2), titanium oxide (TiO
2), aluminium oxide (Al
2O
3) in any one or multiple, its quality percentage composition is 0.5～6%; Pore former is selected from water (H
2O), ethanol, glycerine, ethylene glycol, molecular weight be in 400～1000 the polyethylene glycol (PEG) any one or multiple, its quality percentage composition is 0.5～8%; Solvent is selected from any one in DMF (DMF), DMA (DMAC), 1-METHYLPYRROLIDONE (NMP), the dimethyl sulfoxide (DMSO) (DMSO), and its quality percentage composition is 56～91%.
(2) double-layer coextrusion goes out integrated film forming: adopt from inside to outside to be followed successively by core liquid runner (A), the casting solution runner (B) of the first polymer film, three flow passage structure spinning heads of the casting solution runner (C) of the second polymer film, spinning head discharging opening cross-section structure as shown in Figure 2, the yarn fibre is arranged in parallel in the casting solution runner that passes spinning head, the casting solution of the first polymer film and the second polymer film is injected respectively the casting solution runner of the first polymer film of spinning head and the casting solution runner of the second polymer film, the yarn fibre that is used for strengthening is arranged in parallel and passes in the casting solution runner, under the acting in conjunction of core liquid and coagulating bath, double-deck synchronously coextrusion, by coagulating bath, furl the fine double-tube type filter membrane that strengthens of integrated yarn on again.In preparation process, the yarn fibre can only pass the casting solution runner (Fig. 2-1) of spinning head the first polymer film, the yarn fibre can only pass the casting solution runner (Fig. 2-2) of spinning head the second polymer film, all there is the yarn fibre to pass the casting solution runner of spinning head the first polymer film and the casting solution runner of the second polymer film (Fig. 2-3), can makes respectively Fig. 1-1, Fig. 1-2, the represented double-tube type filter membrane of Fig. 1-3.
As preferably, described yarn fibre is symmetrically distributed in the first polymer film or in the second polymer film, preferred quantity is 3～12.Any one or the mixed yarn more than two kinds that the yarn fiber material is selected from cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber, the glass fibre are fine, are distributed in the first polymer film or the yarn fibre in the second polymer film can be identical or different.Described core liquid is water or water/solvent liquid, and temperature is 20～60 ℃, and solvent is any one in DMF, DMA, 1-METHYLPYRROLIDONE, the dimethyl sulfoxide (DMSO) in the mixed liquor, and its quality percentage composition is 5～30%; Described solidification liquid is water or water/solvent liquid, temperature is 20～60 ℃, and solvent is DMF, N in the mixed liquor, in N-dimethylacetylamide, 1-METHYLPYRROLIDONE, the dimethyl sulfoxide (DMSO) any one, its quality percentage composition is 5～30%.
The casting solution of described yarn fibre and the first polymer film and the second polymer film is finally synchronously from the spinning head coextrusion, and namely the coil stripping speed of the discharging speed of casting solution and yarn fibre is consistent, is 5～30 m/mins, has realized continuous one-step method film forming.
(3) post processing of double-tube type filter membrane: after the film coil stripping is collected, placed 5～80 ℃ of water soaking and washing 24 hours, then (glycerol content is 1～50wt%) immersion 24 hours to place 5～80 ℃ of glycerin/water mixed liquors, dry under 30 ℃, obtain the fine double-tube type filter membrane that strengthens of yarn of structure and stable performance.
The fine performance measurement that strengthens the double-tube type filter membrane of yarn: film size and surface/section structure are measured (SEM) by field emission scanning electron microscope SIRION～100; Water flux adopts homemade flux measuring device to measure, and namely measures 25 ℃, interior pressure or the external pressure pure water transit dose of elementary membrane area in the 0.1MPa lower unit interval of pressure; Mechanical property is measured by electronic tensile machine REGER RWT10; Pressure when the anti-burst performance is broken in ability of swimming pressure process by film characterizes.
Following examples describe the present invention, but described embodiment is not construed as limiting the invention.
Concrete steps:
The preparation of the casting solution of (1) first polymer film: be that (PVC 1300,12wt%), molecular weight is 4 * 10 for 1300 PVC with the degree of polymerization
4PVP (PVP K30,1.2wt%), PEG400 (4wt%), H
2O (0.5wt%), DMAC (82.3wt%) filter 70 ℃ of lower deaeration set aside for use 70 ℃ of lower stirrings after 24 hours; The preparation of the casting solution of the second polymer film: be that (PVC 1300,18wt%), molecular weight is 4 * 10 for 1300 PVC with the degree of polymerization
4PVP (PVP K30,1.8wt%), PEG400 (4wt%), H
2O (0.5wt%), DMAC (75.7wt%) filter 70 ℃ of lower deaeration set aside for use 70 ℃ of lower stirrings after 24 hours.
(2) double-layer coextrusion goes out integrated film forming: polyester fine (6) is penetrated the casting solution runner (B) of the first polymer film of spinning head, be fixed in advance film silk gathering-device along spinning threadling.Core liquid (40 ℃ of H
2O), the casting solution of the first polymer film and the casting solution of the second polymer film inject respectively the core liquid runner (A) of spinning head, the casting solution runner (B) of the first polymer film and the casting solution runner (C) of the second polymer film under pressure simultaneously, then enters coagulating bath (40 ℃ of H with the fine coextrusion of polyester
2O), spinning speed is 20 m/mins.
(3) post processing of double-tube type filter membrane: after the film coil stripping is collected, placed 40 ℃ of water soaking and washing 24 hours, then place 40 ℃ of glycerin/water mixed liquors (glycerol content 20wt%) to soak 24 hours, dry under 30 ℃, namely obtain the fine double-tube type filter membrane that strengthens of yarn, then carry out performance test.
The following form of the design parameter of masking:
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
Embodiment 4
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
Embodiment 5
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
Embodiment 6
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
Embodiment 7
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
Embodiment 8
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
Embodiment 9
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
Embodiment 10
Concrete steps are with embodiment 1, the following form of the design parameter of masking:
The performance parameter of the fine enhancing of the yarn that embodiment 1～10 makes double-tube type filter membrane is as follows:
Above-described embodiment only is not used in for explanation the present invention and limits the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a yarn fibre strengthens the double-tube type filter membrane, it is characterized in that: described tubular filter film is double-decker, internal layer is the first polymer film, skin is the second polymer film, be distributed with for the yarn that strengthens fine in the described tubular filter film, the external diameter of described tubular filter film is 0.8～5.0mm, and internal diameter is 0.4～3.0mm.
2. yarn fibre according to claim 1 strengthens the double-tube type filter membrane, and it is characterized in that: the polymeric material of described the first polymer film and the second polymer film is similar polymers or non-similar polymers.
3. yarn fibre according to claim 2 strengthens the double-tube type filter membrane, and it is characterized in that: described polymeric material is selected from any one in Kynoar, polyvinyl chloride, polyether sulfone, polysulfones, polyacrylonitrile, the cellulose acetate.
4. the fine double-tube type filter membrane that strengthens of yarn according to claim 1, it is characterized in that: described yarn fibre only is distributed in the first polymer film, or only is distributed in the second polymer film, or is distributed in the first polymer film and in the second polymer film.
5. the fine double-tube type filter membrane that strengthens of yarn according to claim 1 is characterized in that: described yarn fibre is symmetrically distributed in the first polymer film or in the second polymer film.
6. yarn fibre according to claim 1 strengthens the double-tube type filter membrane, it is characterized in that: the fine quantity of described yarn is 3～12.
7. each described yarn fibre strengthens the double-tube type filter membrane according to claim 1-6, it is characterized in that: any one or the mixed yarn more than two kinds that described yarn fiber material is selected from cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber, the glass fibre are fine, are distributed in the first polymer film or the yarn fibre in the second polymer film can be identical or different.
8. the fine preparation method who strengthens the double-tube type filter membrane of a yarn is characterized in that may further comprise the steps:
(1) casting solution of preparation the first polymer film and the second polymer film, the deaeration set aside for use;
(2) casting solution of the first polymer film and the second polymer film is injected respectively the casting solution runner of the first polymer film of spinning head and the casting solution runner of the second polymer film, the yarn fibre that is used for strengthening is arranged in parallel and passes in the casting solution runner, under the acting in conjunction of core liquid and coagulating bath, by the solution phase conversion method, the fine double-tube type filter membrane that strengthens of double-deck synchronously coextrusion resultant yarn; Described spinning head is three flow passage structures, from inside to outside is followed successively by the casting solution runner of core liquid runner, the first polymer film, the casting solution runner of the second polymer film;
(3) the double-tube type filter membrane of coextrusion through rolling, clean, dry after, obtain the fine double-tube type filter membrane that strengthens of yarn of structure and stable performance.
9. yarn fibre according to claim 8 strengthens the preparation method of double-tube type filter membrane, it is characterized in that: the yarn fibre described step 2) only passes the casting solution runner of the first polymer film, or only pass casting solution runner in the second polymer film, or all there is the yarn fibre to pass the casting solution runner of the first polymer film and the casting solution runner of the second polymer film.
10. each described yarn fine enhancing double-tube type filter membrane application in external-compression type filtration system or inner pressed filtration system of claim 1-7.
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| CN104815563A (en) * | 2015-04-20 | 2015-08-05 | 天津工业大学 | Reinforced hollow fibrous membrane and preparation method thereof |
| CN107961681A (en) * | 2016-10-18 | 2018-04-27 | 浙江省化工研究院有限公司 | A kind of method for improving Pvdf Microporous Hollow Fiber Membrane intensity |
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| CN103263807A (en) * | 2013-05-21 | 2013-08-28 | 张永安 | Strong water-absorbing composite filtering strip used for filter |
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| CN110732246A (en) * | 2019-09-10 | 2020-01-31 | 梧州中科鼎新工业技术研究院(有限合伙) | acid-resistant hollow fiber nanofiltration membrane and preparation method thereof |
| CN111013249A (en) * | 2019-12-26 | 2020-04-17 | 山东国大黄金股份有限公司 | Carbon fiber composite fiber filter screen |
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