CN108273398A

CN108273398A - Antimicrobial form hollow-fibre membrane and its preparation method and application

Info

Publication number: CN108273398A
Application number: CN201710683102.1A
Authority: CN
Inventors: 吴长江; 奚振宇; 任鹏飞; 杨永强
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-01-05
Filing date: 2017-08-11
Publication date: 2018-07-13
Also published as: CN117619161A; CN108273392A; CN108273392B; CN108273399B; CN108273399A; CN108273386A; CN117379992A

Abstract

The present invention relates to doughnut field of membrane preparation, and in particular, to a kind of antimicrobial form hollow-fibre membrane and its preparation method and application.This method includes：(1) in alkaline solution, the filament for being mixed with filamentary silver is subjected to activation process, the filament activated；(2) filament by the activation is mixed with preparation liquid, and gained mixture is woven, and obtains woven hollow fiber pipe；(3) the woven hollow fiber pipe is shaped to antimicrobial form hollow-fibre membrane.Antimicrobial form hollow-fibre membrane made from method by using the present invention, higher anti-microbial property is kept when it can be long, and under preferred embodiment, the backwash membrane fracture pressure of the antimicrobial form hollow-fibre membrane enhancing of gained, it is seen that the binding ability of its supporting layer and separating layer is strong.

Description

Antimicrobial form hollow-fibre membrane and its preparation method and application

Technical field

The present invention relates to doughnut field of membrane preparation, and in particular, to a kind of antimicrobial form hollow-fibre membrane and its preparation Methods and applications.

Background technology

Membrane separation technique is widely used in water treatment field.Wherein, Kynoar is a kind of high comprehensive performance Membrane material, it has higher tensile strength and excellent chemical stability, corrosion resistance and heat resistance, therefore is commonly used for micro- The material of the seperation films such as filter, ultrafiltration and nanofiltration.With the development of membrane technology, Kynoar wastewater treatment, biologic medical and The fields such as food manufacturing receive more and more attention.

But due to the hydrophobicity of Kynoar, make it in use, the microorganisms such as bacterium are easy in film table Face absorption is proliferated and causes biological pollution, membrane flux can be caused to be greatly lowered, and causes deterioration, the production water water of membrane separating property The reduction of matter and the shortening of membrane lifetime.Therefore main side particularly important to the prevention of biological pollution in UF membrane field, current Method includes：It is continuously passed through chlorine in staying water to be sterilized, but influent quality can be polluted；Or it will be pending Water body filtration goes microorganism in water removal, so again so that flow process is more cumbersome；Or in the process of running, periodically frequently add Enter the oxidants such as sodium hypochlorite, sterilization treatment is carried out to membrane module, kills microorganism, but frequent chemical cleaning can be to film knot It is configured to destroy, reduces the service life of film.Therefore, it is particularly significant to prepare itself seperation film with anti-microbial property.

CN103933867A discloses a kind of preparation method of the PVC hollow-fibre membranes with biocidal property, and this method uses Ultrasonic method disperses nano silver particles in preparation liquid, and silver particles are embedded in hollow-fibre membrane by inversion of phases when forming a film.In addition, CN103285740A discloses a kind of preparation method of antibacterial double-layer hollow fiber film, and silver ion is loaded to molecular sieve by this method It is interior, it is then doped in preparation liquid, prepares the hollow-fibre membrane of film surface enrichment silver molecular sieve.But obtained by the above method Film during long-term operation, as antibacterial material silver fixation simultaneously it is unstable, cause it in the process of running, resist Fungus matter can be constantly lost in, and caused the anti-microbial property of film to decline and even disappeared.

Invention content

The purpose of the present invention is to provide endurable antimicrobial form hollow-fibre membrane of a kind of antibiotic property and preparation method thereof and Using.

The first kind as the present invention is invented, as follows：

To achieve the goals above, one aspect of the present invention provides a kind of preparation method of antimicrobial form hollow-fibre membrane, the party Method includes：

(1) in alkaline solution, the filament for being mixed with filamentary silver is subjected to activation process, the filament activated；

(2) filament by the activation is mixed with preparation liquid, and gained mixture is woven, and obtains doughnut volume Knit pipe；

(3) the woven hollow fiber pipe is shaped to antimicrobial form hollow-fibre membrane；

Wherein, the preparation liquid contains film forming polymer, pore-foaming agent and additive A；The additive A is polyalcohol sum number Average molecular weight is less than one or more in 1,000 polyvalent alcohol.

Second aspect of the present invention provides the antimicrobial form hollow-fibre membrane made from the above method.

Third aspect present invention offer includes the membrane bioreactor of above-mentioned antimicrobial form hollow-fibre membrane.

Fourth aspect present invention provides application of the above-mentioned antimicrobial form hollow-fibre membrane in UF membrane.

Antimicrobial form hollow-fibre membrane made from method by using the present invention keeps higher antibacterial when can be long Performance, and under preferred embodiment, the backwash membrane fracture pressure of the antimicrobial form hollow-fibre membrane enhancing of gained, it is seen that its The binding ability of supporting layer and separating layer is strong；Also, higher water flux and higher fracture strength can also be had both, is suitable for Membrane bioreactor.

The second class as the present invention is invented, as follows：

The first aspect of second class invention provides a kind of method of modifying of hollow woven tube, including uses and include polyphenol The modified solution of compound and cross-linked polymer is modified processing to hollow woven tube.

Preferably, the modified solution is formulated by buffer solution, polyphenolic substance and cross-linked polymer, more preferably Ground, the buffer solution are selected from Tris buffer solutions, PBS buffer solutions or acetic acid/sodium acetate buffer solution.

Preferably, the polyphenolic substance is selected from catechol, tannic acid, dopamine, catechin, gallic acid and green tea At least one of at least one of extract, preferably catechol, tannic acid and dopamine；The cross-linked polymer is selected from Polyvinyl lactam, polyethylene glycol, polyvinylpyrrolidone, chitosan, polyethyleneimine, polyethylene polyamine, tetraethylenepentamine, two In at least one of ethylene triamine, ethylenediamine and hexamethylene diamine, preferably polyethyleneimine, polyethylene glycol and diethylenetriamine extremely Few one kind；The hollow fiber conduit is by polyester fiber, Fypro, polyolefine fiber, polyester fiber, polyurethane fiber, poly- At least one of sulfone fiber or glass fibre are worked out, and are preferably worked out by polyester fiber and/or Fypro.

Preferably, in the modified solution, a concentration of 0.5wt%-15wt% of polyphenolic substance, preferably 3wt%- 15wt%；A concentration of 5wt%-20wt% of cross-linked polymer, preferably 8wt%-18wt%.

Preferably, the temperature of modification is 40 DEG C -80 DEG C, and preferably 50 DEG C -70 DEG C, the time is -60 minutes 10 minutes.

The second aspect of second class invention provides a kind of preparation method of hollow-fibre membrane, including：

Step A is modified processing using the above method to the hollow woven tube as backing material；

Step B, with salting liquid to the hollow woven tube after processing of step A is carried out mineralising processing；

Step C, with preparation liquid, to step B, treated that hollow woven tube carries out surface coating.

Preferably, before step A, hollow woven tube is pre-processed using lye, the lye is preferably selected from alkali The concentration of the aqueous solution of metal hydroxides and alkaline earth metal hydroxide, the lye is preferably 5wt%-20wt%.

Preferably, the salting liquid is selected from CaCl₂Solution, FeCl₃Solution, CuCl₂Solution and AgNO₃In solution at least The mass concentration of one kind, the salting liquid is preferably 0.5%-5%, more preferably 1.5%-5%.

Preferably, polyphenolic substance is contained in the preparation liquid, the polyphenolic substance is preferably selected from catechol, tannin At least one of acid, dopamine, catechin, gallic acid and green-tea extract, be more preferably selected from catechol, tannic acid and At least one of dopamine.

Preferably, Kynoar, additive and solvent are also contained in the preparation liquid；Preferably, in the preparation liquid In, a concentration of 8wt%-26wt% of Kynoar, more preferably 10wt%-20wt%；A concentration of 3wt%- of additive 17.5wt%, more preferably 3.5wt%-10wt%；A concentration of 3wt%-13wt% of polyphenolic substance, more preferably 3.5wt%-10wt%.

Preferably, the additive is selected from polyvinylpyrrolidone, the molecular weight 1000- of molecular weight 3000-50000 In the polyvinyl alcohol of 10000 polyethylene glycol, the polyethylene oxide of molecular weight 10000-60000 and molecular weight 8000-50000 At least one, the solvent are selected from n,N-Dimethylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone at least It is a kind of.

Preferably, in step B, soaking temperature is 10-40 DEG C, preferably 25-35 DEG C；Soaking time is -8 hours 1 hour, excellent It selects -5 hours 3 hours.

Third class as the present invention is invented, as follows：

The first aspect of the third class invention of the present invention provides a kind of preparation method of hollow-fibre membrane, including：

1) contg. silver fiber beam and polymer fiber Shu Jinhang are woven, to obtain contg. silver fiber woven tube；

2) the contg. silver fiber woven tube for obtaining step 1) is coextruded with casting solution and core liquid, is then separated, with Obtain the hollow-fibre membrane.

Preferably, the polymer fiber beam is that 100-1000 root filaments form by number；Contg. silver fiber beam is by number It is formed for the filament of 1-10 root argentiferous.

Preferably, it is fine to be selected from polyester fiber, Fypro, polyolefine fiber, polyester fiber, polyurethane for the filament At least one of dimension, polysulfone fibre or glass fibre, preferably polyester fiber and/or Fypro.

Preferably, the casting solution used in step 2) includes Kynoar, solvent, non-solvent and additive.

Preferably, the Kynoar number-average molecular weight is 100,000-50 ten thousand；Preferably, described in the casting solution The mass content of Kynoar is 10%-30%, more preferably 15%-25%.

Preferably, the additive is selected from polyvinylpyrrolidone, the molecular weight 1000- of molecular weight 3000-50000 In the polyvinyl alcohol of 10000 polyethylene glycol, the polyethylene oxide of molecular weight 10000-60000 and molecular weight 8000-50000 It is at least one；Preferably, in the casting solution, the mass content of the additive is 2%-20%, more preferably 5%- 15%.

Preferably, the solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone At least one of；Preferably, in the casting solution, the mass content of the solvent is 50%-80%, more preferably 60%-75%.

Preferably, the non-solvent is at least one of propylene glycol, glycerine, triethylene glycol and polyethylene glycol, described poly- Ethylene glycol is preferably selected from least one of polyethylene glycol 200, polyethylene glycol 400 and Macrogol 600；Preferably, described In casting solution, the mass content of the non-solvent is 5%-20%, more preferably 8%-12%.

Preferably, the temperature of the coagulating bath is controlled at 30 DEG C -80 DEG C, preferably 50 DEG C -70 DEG C；The temperature of the core liquid Control is at 20 DEG C -80 DEG C, preferably 20 DEG C -60 DEG C.

Preferably, the hollow-fibre membrane is subjected to hydrophiling post-processing, the hydrophiling post-processing after step 2) For：The hollow-fibre membrane that step 2) is obtained impregnates -24 hours 2 hours in 40 DEG C -90 DEG C of water, carries out hydrophiling and fenestra Sizing post-processing；By the hollow-fibre membrane after hydrophilicity-imparting treatment in 20 DEG C of -60 DEG C of dryings -48 hours 2 hours, just obtained after dry Have both the hollow fiber ultrafiltration membrane of high mechanical properties and anti-microbial property.

Description of the drawings

Fig. 1 is the SEM figures of the antimicrobial form hollow-fibre membrane obtained by the embodiment 1-1 of the first invention of the present invention.

Fig. 2 is according to a kind of preferred embodiment of the second class invention of the present invention there is the PVDF of strong interfacial tension to increase The schematic diagram of strong type hollow-fibre membrane.

Fig. 3 is the cross-section morphology structure chart according to the hollow-fibre membrane of one embodiment of the second class invention of the present invention.

Fig. 4 is the surface topography figure according to the hollow-fibre membrane of one embodiment of the second class invention of the present invention.

Fig. 5 is the hollow-fibre membrane obtained according to a kind of preparation method of embodiment of the third class invention of the present invention Schematic diagram.

Fig. 6 is that the hollow-fibre membrane obtained according to a kind of preparation method of embodiment of the third class invention of the present invention exists Stereoscan photograph after being impregnated 12 hours in Escherichia coli solution.

Specific implementation mode

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

In the first kind invention of the present invention：

One aspect of the present invention provides a kind of preparation method of antimicrobial form hollow-fibre membrane, and this method includes：

According to the present invention, the present invention by filamentary silver with film forming filament by being combined and using additive A, energy in preparation liquid Enough so that filamentary silver is stabilized in the antimicrobial form hollow-fibre membrane, to constantly play anti-microbial property, Er Qietong for a long time When can also enhance gained antimicrobial form doughnut film strength.

Although the content of the filamentary silver being mixed in the filament of filamentary silver can change in wider range, it is contemplated that Filamentary silver is combined maximally efficiently, it is preferable that relative to 100 filaments (film forming filament), the quantity of the filamentary silver is 2- 50, preferably 5-20 roots.

Preferably, the fiber number of the filamentary silver is 10-500D, preferably 50-300D, more preferably 100-200D.The filamentary silver The method that this field routine may be used is made, and can also be commercially available product, and to this present invention, there is no particular limitation.

Wherein, the filament for being mixed with filamentary silver is preferably made of the filamentary silver and film forming filament, described at membrane fiber Silk can be the silk of the conventional any fiber that supporting layer hollow woven tube is formed when being used to prepare hollow-fibre membrane in this field, example If the film forming filament is polyester fiber, Fypro, polyolefine fiber, polyester fiber, polyurethane fiber, polyvinylidene fluoride It is one or more in alkene fiber, polysulfone fibre and glass fibre.In view of the method institute of the film forming filament and the present invention The filamentary silver and preparation liquid of use have preferably mating reaction, to obtain the more excellent antimicrobial form hollow-fibre membrane of performance, Preferably, the filament is polyester fiber and/or Fypro.The filament can be commercially available product, can also use this Prepared by the method for field routine, there is no particular limitation to this by the present invention.

Wherein it is preferred to which the filametntary fiber number of film forming is 10-500D, preferably 50-300D, more preferably 100- 200D.It is preferably solid long filament.

According to the present invention, in step (1), by the way that the filament for being mixed with filamentary silver is carried out activation process in alkaline solution, The oil stain being mixed on the filament of filamentary silver or surfactant etc. can be removed, also allows for that treated and be mixed with the filament of filamentary silver Subsequent processing can preferably be carried out.

Alkali compounds in the alkaline solution can be to realize any alkalization that activation is realized to filament Close object, it is preferable that the alkali compounds in the alkaline solution is alkali metal hydroxide, alkaline earth metal hydroxide, alkali gold Belong to one or more in carbonate, alkali metal hydrogencarbonate and ammonia, more preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, It is one or more in calcium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, saleratus and ammonia.

Wherein, the content of the alkali compounds in the alkaline solution can change in wider range, in order to obtain more Good activation effect, it is preferable that the content of the alkali compounds in the alkaline solution is 5-20 weight %, preferably 5-15 weights Measure %.

According to the present invention, in step (1), the filament for being mixed with filamentary silver can partly, substantially entirely or entirely It is immersed in portion in the alkaline solution, in order to enable the filament for being mixed with filamentary silver can be activated more fully, preferably It fully immerses into the alkaline solution.Wherein, the dosage of the alkaline solution can change in wider range, as long as energy Enough pair makes the filament for being mixed with filamentary silver partly, substantially entirely or fully be immersed, the present invention couple There is no particular limitation for this.

In the case of, according to the invention it is preferred to, the condition of the activation process includes：Temperature is 30-80 DEG C, time 10- 50min.It is highly preferred that the condition of the activation process includes：Temperature is 30-70 DEG C, time 15-30min.

According to the present invention, which can also include, the filament after activation process is cleaned (such as use water Wash), then centrifuge dripping (such as centrifuge dripping 10-30min under the rotating speed of 3,000-10,000rpm), to be activated Filament.

According to the present invention, the preparation liquid contains film forming polymer, pore-foaming agent and additive A, for wetting fibre silk, And separating layer first is formed in film forming procedure, combination stability of the filamentary silver in gained film can be enhanced.

Wherein, the various polymer for being used to form separating layer of this field routine may be used in the film forming polymer, but Be in order to increase and the step (1) of the present invention obtained by filament between binding performance, it is preferable that the film forming polymer is It is one or more in Kynoar (PVDF), polyether sulfone (PES) and polyacrylonitrile (PAN).Preferably, the film-forming polymer The number-average molecular weight of object is 10-50 ten thousand.

Wherein, the conventional pore-foaming agent being used in preparation liquid in this field, for example, polyethylene may be used in the pore-foaming agent Pyrrolidones (PVP), polyethylene glycol (PEG), polyethylene oxide, polyvinyl alcohol, polymethyl methacrylate and polyvinyl acetate It is one or more in ester, preferably number-average molecular weight be 3,000-50,000 polyvinylpyrrolidone, molecular weight 1,000-10, 000 polyethylene glycol, the polyethylene oxide of molecular weight 10,000-60,000, molecular weight 8,000-50,000 polyvinyl alcohol and It is one or more in the polymethyl methacrylate of molecular weight 11,000-85,000.It is equal that the above molecular weight is commonly referred to as number Molecular weight.

Wherein, the additive A is preferably propylene glycol, glycerine, triethylene glycol, the poly- second that number-average molecular weight is 200-800 Glycol, polypropylene glycol, polyvinylpyrrolidone, polyvinyl butyral and the polyvinyl acetate that number-average molecular weight is 200-800 It is one or more in ester.

According to the present invention, although the preparation liquid contains the film forming polymer, pore-foaming agent and additive A and can pass through institute State the performance that antimicrobial form hollow-fibre membrane is promoted in mating reaction between film forming polymer, pore-foaming agent and additive A, but in order to The synergistic effect between the film forming polymer, pore-foaming agent and additive A is improved, in order to enable preparation liquid can be with step (1) There is stronger binding ability between the filament of gained, it is preferable that in the preparation liquid, the film forming polymer, pore-foaming agent Weight ratio with additive A is 100：15-70：20-150, preferably 100：20-60：30-100, more preferably 100：25-40： 40-70。

According to the present invention, solvent in the preparation liquid preferably uses the benign molten of the film forming polymer and pore-foaming agent Agent, preferably N, N '-dimethyl formamide, N, N '-dimethyl acetamide, N-Methyl pyrrolidone, triethyl phosphate, ring fourth It is one or more in sulfone, dimethyl sulfone and benzophenone.Wherein it is preferred to the weight of the film forming polymer and the solvent Than being 1：2-8, preferably 1：3-6.

In accordance with the present invention it is preferred that the preparation liquid also contains polyphenol compound, the polyphenol compound is formula It is (1) one or more in compound represented, tannic acid, formula (2) compound represented and green-tea extract, wherein

R¹-R⁶In at least 2 be OH, it is remaining to be each independently H, halogen ,-L-COOM ,-L-SO₃M、-L-NH₂、- The alkylthio group of the alkyl of L-OH, C1-C6, the alkoxy of C1-C6 or C1-C6；R⁷-R¹⁰And R¹³-R¹⁷In at least 2 be OH, remain Remaining R⁷-R¹⁰And R¹³-R¹⁷And R¹¹-R¹²It is each independently H, halogen ,-L-COOM ,-L-SO₃M、-L-NH₂、-L-OH、C1- The alkylthio group of the alkyl of C6, the alkoxy of C1-C6 or C1-C6；Each L is each independently selected from the alkylidene of C0-C6；Each M It is each independently H and alkali metal element.

Wherein, the specific example of the alkyl of C1-C6 for example can be：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, Isobutyl group, tertiary butyl, n-pentyl, n-hexyl etc..

The specific example of the alkoxy of C1-C6 for example can be：Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, just Butoxy, isobutoxy, tert-butoxy, n-pentyloxy, positive hexyloxy etc..

The specific example of the alkylthio group of C1-C6 for example can be：Methyl mercapto, ethylmercapto group, positive rosickyite base, isopropyisulfanyl, just Butylthio, isobutylthio, tertiary butylthio, positive penta sulfenyl, just own sulfenyl etc..

The halogen for example can be F, Cl, Br, I.

The alkali metal element for example can be Li, Na, K.

The specific example of the alkylidene of C0-C6 for example can be：The alkylidene ,-CH of C0₂-、-CH₂CH₂-、- CH₂CH₂CH₂-、-CH(CH₃)CH₂-、-CH₂CH(CH₃)-、-CH₂CH₂CH₂CH₂-、-CH(CH₃)CH₂CH₂-、-C(CH₃)₂CH₂-、- CH(CH₂CH₃)CH₂-、-CH₂CH(CH₃)CH₂-、-CH₂C(CH₃)₂-、-CH₂CH(CH₂CH₃)-、-CH₂CH₂CH(CH₃)-、-CH (CH₂CH₃CH₃)-、-CH(CH(CH₃)CH₃)-、-CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂Etc..Wherein, the Asia of C0 Alkyl indicates that the linking group is not present or indicates connecting key, and thus the group at the linking group both ends is connected directly.

Preferably, R¹-R⁶In at least 2 be OH, it is remaining to be each independently H, halogen ,-L-COOM ,-L-SO₃M、- L-NH₂,-L-OH, the alkyl of C1-C4, the alkoxy of C1-C4 or C1-C4 alkylthio group；R⁷-R¹⁰And R¹³-R¹⁷In at least 2 For OH, remaining R⁷-R¹⁰And R¹³-R¹⁷And R¹¹-R¹²It is each independently H, halogen ,-L-COOM ,-L-SO₃M、-L-NH₂、- The alkylthio group of the alkyl of L-OH, C1-C4, the alkoxy of C1-C4 or C1-C4；Each L is each independently selected from the alkylene of C0-C4 Base；Each M is each independently H, Na and K.

It is highly preferred that R¹-R⁶In at least 2 be OH, it is remaining to be each independently H, F, Cl, Br ,-COOM ,-CH₂- COOM、-CH₂CH₂-COOM、-CH₂CH₂CH₂-COOM、-CH(CH₃)CH₂-COOM、-CH₂CH(CH₃)-COOM、- CH₂CH₂CH₂CH₂-COOM、-SO₃M、-CH₂-SO₃M、-CH₂CH₂-SO₃M、-CH₂CH₂CH₂-SO₃M、-CH(CH₃)CH₂-SO₃M、- CH₂CH(CH₃)-SO₃M、-CH₂CH₂CH₂CH₂-SO₃M、-NH₂、-CH₂-NH₂、-CH₂CH₂-NH₂、-CH₂CH₂CH₂-NH₂、-CH (CH₃)CH₂-NH₂、-CH₂CH(CH₃)-NH₂、-CH₂CH₂CH₂CH₂-NH₂、-OH、-CH₂-OH、-CH₂CH₂-OH、-CH₂CH₂CH₂- OH、-CH(CH₃)CH₂-OH、-CH₂CH(CH₃)-OH、-CH₂CH₂CH₂CH₂- OH, methyl, ethyl, n-propyl, isopropyl, positive fourth It is base, isobutyl group, sec-butyl, tertiary butyl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, secondary Butoxy, tert-butoxy, methyl mercapto, ethylmercapto group, positive rosickyite base, isopropyisulfanyl, positive butylthio, isobutylthio, secondary butylthio or Tertiary butylthio.

According to the present invention, in a kind of preferred embodiment of the present invention, formula (1) compound represented is selected from following formula Compound represented：

In a kind of preferred embodiment of the present invention, formula (2) compound represented is selected from chemical combination shown in following formula Object：

Wherein, the green-tea extract can be the green-tea extract extracted by this field traditional extraction means, or The green tea extraction product of Hunan Nutramax Inc. can be available from.

It is particularly preferred that the polyphenol compound is one kind in gallic acid, catechol, tannic acid and dopamine Or a variety of, preferably gallic acid.

In a kind of preferred embodiment of the present invention, the polyphenol compound is gallic acid, and the film forming is poly- Conjunction object is Kynoar, and the pore-foaming agent is polyvinylpyrrolidone, and the additive A is glycerine.It is highly preferred that described Film forming polymer is the Kynoar that molecular weight is 200,000-21 ten thousand, and the pore-foaming agent is that number-average molecular weight is 2.5 ten thousand-3 ten thousand Polyvinylpyrrolidone.

In accordance with the present invention it is preferred that in the preparation liquid, the weight ratio of the film forming polymer and polyphenol compound is 100：10-50, preferably 100：15-40.

According to the present invention, the dosage of the preparation liquid can be preferably such that above-mentioned cellulose energy with the conventional amount used of this field Enough to be all impregnated with the preparation liquid, there is no particular limitation to this by the present invention.

The preparation method that the preparation liquid of this field routine may be used in the preparation of the preparation liquid carries out, such as can be lazy Property atmosphere (nitrogen atmosphere, argon gas atmosphere etc.) in, said components are stirred mixing, and deaeration, to which preparation liquid be made.

It is described to weave the method progress that this field routine may be used according to the present invention, such as by the fiber of the activation Silk introduces the braiding head of woven tube crochet with film liquid mixture, and woven pipe spinning head carries out spinneret braiding, the volume of formation Pipe is knitted to be sent again to woven tube coater to strike off the extra preparation liquid of filament adherency.Obtain leading in wire drawing wheel after woven tube Under gravitation, enters and squeeze out nozzle to be coextruded, wherein the hauling speed of the wire drawing wheel is preferably 0.5-6m/min.

This method can also include：After step (2), gained woven hollow fiber pipe is subjected to solidification and washing process, Wherein, the temperature of the solidification and washing process is preferably 30-80 DEG C.In as obtained by solidifying and washing process can make Hollow fiber woven tube is shaped to film.Wherein, wherein the solidification liquid that uses of solidification processing can be water, or can be containing N, N '-dimethyl formamide (DMF), N, N '-dimethyl acetamide (DMAc), N-Methyl pyrrolidone, triethyl phosphate, ring fourth One or more aqueous solvents in sulfone, dimethyl sulfone and benzophenone (water content is preferably 60 weight % or more).This is solidifying Gu and washing process can be carried out at the same time, i.e., also washed while solidification in solidification liquid, naturally it is also possible to Substep carries out, such as the filament after being solidified in solidification liquid is cleaned in water again.In general, directly in coagulating basin Solidification and washing process are carried out at the same time in solidification liquid.

According to the present invention, the process that the woven hollow fiber pipe is shaped to antimicrobial form hollow-fibre membrane of step (3) The method that routine of the invention may be used carries out, such as may include that can pass through phase separation from solidification and washing process system Obtain antimicrobial form hollow-fibre membrane.

In accordance with the present invention it is preferred that step (3) further includes carrying out the antimicrobial form hollow-fibre membrane of gained at hydrophiling Reason, the condition of the hydrophilic treated include：Using 40-90 DEG C of hot water, 2-24h is impregnated.

According to the present invention, after hydrophilicity-imparting treatment, can also include the film of gained is cleaned it is (such as clear with water Wash), and it is dry (such as in 20-60 DEG C of dry 2-48h).

Higher anti-microbial property is kept when the antimicrobial form hollow-fibre membrane of gained of the invention can be long, and preferred Under embodiment, the backwash membrane fracture pressure of the antimicrobial form hollow-fibre membrane of gained enhancing, it is seen that its supporting layer and separating layer Binding ability is strong；Also, higher water flux can also be had both and higher fracture strength, higher water contact angle, flux are extensive Multiple rate, rejection etc., are suitable for membrane bioreactor.Wherein, sterilizing rate of the antimicrobial form hollow-fibre membrane to Escherichia coli It still is able to keep 80% or more, preferably 85% or more after 240h, the sterilizing rate of Staphylococcus aureus still is able to after 250h Keep 80% or more, preferably 83% or more；Backwash membrane fracture pressure for example can be 2.5MPa or more, preferably 3-6MPa, it is more excellent It is selected as 4-6MPa；Water flux for example can be 150-250L/m²H, preferably 150-200L/m²h；Fracture strength for example can be 15MPa or more, preferably 18-22MPa, more preferably 20-22MPa；Water contact angle for example can be 50-60 degree；Rejection example Such as can be 90% or more.

According to the present invention, the antimicrobial form hollow-fibre membrane can be in food, medicine, biology, environmental protection, chemical industry, metallurgy, energy It is applied in membrane separation technique involved in source, oil, water process, electronics and the fields such as bionical.

In the second class invention of the present invention：

The present invention the second class invention, for hollow-fibre membrane in the prior art in membrane bioreactor application process by In the reasons such as bad mechanical strength cause rupture, fracture of wire situations such as, and UF membrane layer existing for enhancement type hollow fiber film at present Poor adhesion, the shortcomings of being easy to fall off between backing material, the present invention provides a kind of method of modifying of hollow woven tube and A kind of preparation method of doughnut layer.One aspect of the present invention goes out cross-linked stable and shaggy mistake in woven tube surface construction Layer is crossed, on the other hand by the adjustment of preparation liquid component, to prepare the excellent hollow-fibre membrane of boundary strength.

In the first aspect of the invention, a kind of method of modifying of hollow woven tube is provided comprising using comprising more The modified solution of phenolic compounds and cross-linked polymer is modified processing to hollow woven tube.

In the present invention, after above-mentioned modification, modified coating is formd in hollow establishment pipe surface.Modified coating In catechol group and hollow woven tube form hydrophobic effect, and cross-linked structure strengthens the combination of modified coating and woven tube Stabilized soil pavement, while modified coating surface introduces amino and hydroxyl isopolarity group, is conducive to improve transition zone and membrane material Compatibility between material.

According to the preferred embodiment of the present invention, before the modification, hollow woven tube is carried out in advance with lye Processing.Preferably, the lye is selected from the aqueous solution of alkali metal hydroxide and alkaline earth metal hydroxide, more preferable hydroxide The aqueous solution of sodium, such as sodium hydroxide solution.In one embodiment, a concentration of 5wt%-20wt% of the lye.It is described Pretreatment can carry out such as -60 minutes 5 minutes at a temperature of 20 DEG C -60 DEG C.

In one embodiment, it is described with lye to hollow woven tube carry out pretreatment specifically include：By hollow woven tube Immerse 5wt%-20wt% sodium hydroxide solution in, handled -30 minutes 5 minutes at a temperature of 20 DEG C -60 DEG C, then spend from Sub- water cleaning, with 3000-10000 revs/min of speed centrifuge dripping, processing time is -20 minutes 5 minutes.

According to the preferred embodiment of the present invention, the modified solution is by buffer solution and polyphenolic substance and cross-linked polymeric Object is formulated.Preferably, it is molten to be selected from Tris buffer solutions, PBS buffer solutions or acetic acid/acetate buffer for the buffer solution Liquid.

According to the preferred embodiment of the present invention, the polyphenolic substance is selected from catechol, tannic acid, dopamine, youngster At least one at least one of theine, gallic acid and green-tea extract, preferably catechol, tannic acid and dopamine Kind.Preferably, a concentration of 0.5wt%-15wt% of polyphenolic substance, preferably 3wt%-15wt%.

In one embodiment, the polyphenolic substance is catechol, preferably its concentration 5wt%-15wt%.Another In a embodiment, the polyphenolic substance is tannic acid, preferably its a concentration of 1wt%-10wt%.In yet another embodiment, The polyphenolic substance is dopamine, preferably its a concentration of 0.5wt%-8wt%.

According to the preferred embodiment of the present invention, the cross-linked polymer is selected from polyvinyl lactam, polyethylene glycol, polyethylene In pyrrolidones, chitosan, polyethyleneimine, polyethylene polyamine, tetraethylenepentamine, diethylenetriamine, ethylenediamine and hexamethylene diamine At least one, preferably at least one of polyethyleneimine, polyethylene glycol and diethylenetriamine.Preferably, cross-linked polymer A concentration of 5wt%-20wt%, preferably 8wt%-18wt%.

According to the preferred embodiment of the present invention, the hollow fiber conduit is fine by polyester fiber, Fypro, polyolefin At least one of dimension, polyester fiber, polyurethane fiber, polysulfone fibre or glass fibre are worked out, preferably by polyester fibre Dimension and/or Fypro are worked out.

In some embodiments, the internal diameter of the hollow woven tube is 0.7mm-1.5mm, outer diameter 1.0mm-2.3mm. In some embodiments, the establishment density of the hollow woven tube is 15.5mm-17.5mm, grammes per square metre 1.0g/mm-1.6g/mm.

According to the preferred embodiment of the present invention, the temperature of modification is 40-80 DEG C, and preferably 50-70 DEG C, the time is 10-60 minutes.In one embodiment, the modification includes：Polyphenolic substance, cross-linked polymer and buffer solution are existed It is mixed at room temperature, hollow woven tube is dipped into modified solution, handle 10-60 minutes at a temperature of 50 DEG C -70 DEG C, so It is cleaned afterwards with deionized water, centrifuge dripping.

In the second aspect of the invention, a kind of preparation method of hollow-fibre membrane is provided comprising：

Step A, using method of modifying described above to being modified processing to hollow woven tube；

Step B carries out mineralising processing with salting liquid to the hollow woven tube after processing of step A；And

In the method for the invention, it since catechol group has reproducibility, is handled by the mineralising of salting liquid, energy It is enough to grow nano particle in braiding pipe surface.The formation of one side nano particle further increases the phase interaction with UF membrane layer With the increase of, another aspect roughness but also binding site further increases, be conducive to the stabilization of transition zone and separating layer.

According to the preferred embodiment of the present invention, the salting liquid is selected from CaCl₂Solution, FeCl₃Solution, CuCl₂Solution and AgNO₃At least one of solution.The mass concentration 0.5%-5% of the salting liquid, preferably 1.5%-5%.

According to the preferred embodiment of the present invention, the granular size of the nano particle is 15nm-32nm.

According to the preferred embodiment of the present invention, in step B, soaking temperature is 10 DEG C -40 DEG C, preferably 25 DEG C -35 DEG C；Leaching It is -8 hours 1 hour, preferably -5 hours 3 hours to steep the time.

It is preferred that before carrying out step C, by step B, treated that hollow woven tube is cleaned with deionized water, at 60-80 DEG C At a temperature of dry.

According to the preferred embodiment of the present invention, the number-average molecular weight of the Kynoar in the casting solution is 100,000- 500000.

According to the preferred embodiment of the present invention, contain polyphenolic substance in the preparation liquid.Preferably, the polyphenol It closes object and is selected from least one of catechol, tannic acid, dopamine, catechin, gallic acid and green-tea extract, more preferably At least one of catechol, tannic acid and dopamine.

According to the preferred embodiment of the present invention, Kynoar, additive and solvent are also contained in the preparation liquid.

In the preparation liquid, the concentration of Kynoar is preferably 8wt%-26wt%, more preferably 10wt%- 20wt%.

In the preparation liquid, the concentration of additive is preferably 3wt%-17.5wt%, more preferably 3.5wt%- 10wt%.

In the preparation liquid, polyphenolic substance concentration is preferably 3wt%-13wt%, more preferably 3.5wt%- 10wt%.

According to the preferred embodiment of the present invention, the additive is the polyvinylpyrrolidine of molecular weight 3000-50000 Ketone, the polyethylene glycol of molecular weight 1000-10000, the polyethylene oxide of molecular weight 10000-60000 and molecular weight 8000-50000 At least one of polyvinyl alcohol.

According to the preferred embodiment of the present invention, the solvent is n,N-Dimethylformamide, n,N-dimethylacetamide With at least one of N-Methyl pyrrolidone.

In the present invention, the polyphenolic substance in preparation liquid can effectively improve on separating layer and transition zone nano particle with And the adhesion of polar group.

In some embodiments, in step C, by the way that step B treated hollow woven tubes are passed through spinning head, and will Preparation liquid injects spinning head and keeps constant pressure, with the hollow woven tube of fixing wound speed drawing, to make hollow woven tube Surface coats the preparation liquid.

Preferably, the hollow woven tube of the preparation liquid will be coated successively in immersion precipitation slot and rinsing bowl, to be made The hollow-fibre membrane.The hollow-fibre membrane is the woven tube enhancement type hollow fiber film for having high adhesion strength.

Preferably, the spinning head aperture is 1.7mm-2.3mm.Preferably, the winding speed of hollow woven tube is drawn For 2m/min-20m/min.

Preferably, the coagulating bath is water and n,N-Dimethylformamide, n,N-dimethylacetamide and N- methyl pyrroles The mixture of at least one of pyrrolidone, more preferably wherein the mass fraction of water is 60% or more.

In the present invention, the operation temperature of the gel slot and rinsing bowl is 30-80 DEG C.

Preferably, preparation method of the present invention further includes carrying out hollow-fibre membrane obtained above at hydrophiling Reason, such as impregnate carry out within -12 hours 4 hours hydrophilicity-imparting treatment in the hot water, hot water water temperature is 60 DEG C -80 DEG C.

Preferably, the hollow-fibre membrane after hydrophilicity-imparting treatment is cleaned with deionized water, and 12 hours dry at 20-60 DEG C- 36 hours.

Compared with prior art, the present invention the second class advantageous effect of the invention is：

1. the method for modifying of polyphenolic substance used in the present invention and cross-linked polymer, may be implemented in unlike material The processing for weaving pipe surface, special groups and cross-linked structure ensure that the stabilization of modified coating in coating.Simultaneously on modified coating Polar group, be conducive to sticking for Kynoar separating layer.

2. realizing the growth of a variety of nano particles in braiding pipe surface, nano particle is evenly distributed, and when can pass through submergence Between and solution temperature the size and density of nano particle are adjusted.The formation of nano particle effectively increases woven tube and film The interfacial contact area of separating layer, enhances interface bond strength.

3. silver nano-grain can be introduced by the above method, and impart in the braiding tube enhancement type of this kind of method preparation The excellent sterilization bacterial decontamination property of empty fiber membrane, effectively extends the active time of the film.

4. further enhancing the combination of separating layer and transition zone by the way that polyphenolic substance is added in preparation liquid, ensure that this The long-time steady operation of kind hollow membrane.

5. the preparation process of the present invention is simple, raw materials used cheap, be conducive to industrialized production.

In the third class invention of the present invention：

The third class invention of the present invention, in order to solve the above technical problem, the present invention provides a kind of new doughnuts The preparation method of film.The preparation method includes：

According to the preferred embodiment of the present invention, the preparation method further includes before step 1) to the contg. silver fiber And/or polymer fiber is cleaned.According to one embodiment, to the contg. silver fiber and/or gathered with lye and deionized water Fibres are closed to be cleaned.Preferably, the lye is the sodium hydroxide solution of 5%-15%.Preferably, with caustic dip Temperature is -60 minutes 20 minutes, and the time is -30 minutes 5 minutes.

According to the preferred embodiment of the present invention, the preparation method further includes after step 2) by the doughnut Film carries out hydrophiling post-processing.According to a preferred embodiment, the hydrophiling, which post-processes, is：The hollow fibre that step 2) is obtained Dimension film impregnates -24 hours 2 hours in 40 DEG C -90 DEG C of water, carries out hydrophiling and fenestra sizing post-processing；By hydrophilicity-imparting treatment Hollow-fibre membrane afterwards has just obtained having both high mechanical properties and antibacterial in 20 DEG C of -60 DEG C of dryings -48 hours 2 hours after dry The hollow fiber ultrafiltration membrane of performance.

According to the preferred embodiment of the present invention, described to be woven to：By contg. silver fiber beam and polymer fiber beam along core Liquid pipe carries out " people " font and is cross-woven.

Preferably, the polymer fiber beam is that 100-1000 root filaments form by number.Preferably, contg. silver fiber Beam is made of the filament that number is 1-10 root argentiferous.

According to the present invention, the contg. silver fiber beam commercially available can also be made by oneself.

According to the preferred embodiment of the present invention, it is fine to be selected from polyester fiber, Fypro, polyolefin for the filament At least one of dimension, polyester fiber, polyurethane fiber, polysulfone fibre or glass fibre, preferably polyester fiber and/or polyamide Fiber.

According to the preferred embodiment of the present invention, the casting solution used in step 2) include Kynoar, it is solvent, non- Solvent and additive.

According to the preferred embodiment of the present invention, the casting solution is prepared by following steps：By Kynoar, Solvent, non-solvent, additive mixing, are stirred -24 hours 12 hours, vacuum defoamation 12 is small in a kettle at 60 DEG C -120 DEG C When -24 hours, to obtain the casting solution.

Preferably, the number-average molecular weight of the Kynoar is 100,000-50 ten thousand.It is described poly- inclined in the casting solution The mass content of vinyl fluoride is preferably 10%-30%, more preferably 15%-25%.

Preferably, the additive is selected from polyvinylpyrrolidone, the molecular weight 1000- of molecular weight 3000-50000 In the polyvinyl alcohol of 10000 polyethylene glycol, the polyethylene oxide of molecular weight 10000-60000 and molecular weight 8000-50000 It is at least one.In the casting solution, the mass content of the additive is preferably 2%-20%, more preferably 5%-15%.

Preferably, the solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone At least one of.In the casting solution, the mass content of the solvent is preferably 50%-80%, more preferably 60%- 75%.

Preferably, the non-solvent is at least one of propylene glycol, glycerine, triethylene glycol and polyethylene glycol.It is described poly- Ethylene glycol is preferably selected from polyethylene glycol 200, polyethylene glycol 400 and Macrogol 600.In the casting solution, the non-solvent Mass content be preferably 5%-20%, more preferably 8%-12%.

According to the preferred embodiment of the present invention, the core liquid be the solvent mixed solution or water with it is described non-molten The mixed solvent of agent.Preferably, in the core liquid, the weight percent concentration of water is 50%-100%, preferably 70%- 100%.

According to the preferred embodiment of the present invention, the temperature of the core liquid is controlled at 20 DEG C -80 DEG C, preferably 20 DEG C -60 ℃

According to the preferred embodiment of the present invention, by immersing the product of coextrusion institute is carried out in coagulating bath and water-bath State phase separation.The coagulating bath be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone at least A kind of aqueous solution, mass concentration are preferably 0%-40%, more preferably 0%-20%.

According to the preferred embodiment of the present invention, the temperature of the coagulating bath is controlled at 30 DEG C -80 DEG C, preferably 50 DEG C - 70℃。

Compared with prior art, the beneficial effects of the invention are as follows：

1. using fibrage-coextrusion integral process, contg. silver fiber beam and polymer fiber, which are woven into fiber, to be compiled Enhancement layer is knitted, and has been embedded into the ontology of hollow-fibre membrane.Compared to common hollow-fibre membrane, which has higher drawing It stretches intensity and reaches 12.5MPa-50MPa, explosion resistant strength reaches 0.25MPa-1.5MPa, pure water flux 120L/m²h-500L/m²h。

2. the present invention obtains hollow-fibre membrane due to there is the introducing of argentiferous woven tube, imitated with fabulous antibacterial and sterilization Fruit.Experiment shows that the hollow-fibre membrane is 82.5%-93.5%, the suppression to Staphylococcus aureus to the inhibiting rate of Escherichia coli Rate processed is 75.1%-89.7%, has excellent antibacterial action.Meanwhile the hollow-fibre membrane cuts bovine serum albumin(BSA) It is 95.3%-97.3% to stay rate, has excellent separating property.

3. since the argentiferous woven tube of the invention used is wrapped in the inside of Kynoar hollow membrane so that silver particles exist The feature eluted, antibacterial time is grown is not easy during use.

4. the present invention provides a kind of preparation method of the above-mentioned hollow fiber ultrafiltration membrane for having both antibacterial and high mechanical properties, This method is easy to operate, can be realized using existing industrial equipment, is advantageously implemented industrialized production.

It should be understood that although having similar content among the above-mentioned three classes invention of the present invention, the invention of this three classes Description between independently of each other, do not limit each other.

The present invention will be described in detail by way of examples below.

First kind invention offer for the present invention is exemplified below：

In following embodiment and comparative example：

Water flux is measured using the outer press filtering device of dead end, that is, the wet film after cleaning is first in 0.15MPa precompressed Then 30min measures its external pressure water flux in 0.1MPa；It is subsequently passed BSA solution, measures rejection.

What backwash membrane fracture pressure was reacted is the interface bond strength of woven tube and separating layer, is to use water kickback pressure It measures.

Water contact angle is measured by contact angle measurement.

Selected model bacterium is Escherichia coli and staphylococcus aureus in antibacterial tests, is purchased from the enzyme-linked biology in Shanghai Science and Technology Ltd..

Anti-microbial property test method：Film is measured in each embodiment to the antibiotic property of above two bacterium using inhibition zone method Energy.Operation is as follows, on ultra-clean workbench, the Escherichia coli of 100 μ L of absorption or staphylococcus aureus suspension and culture medium 15mL is mixed, and pours into cooling in culture dish and tablet containing bacterium is made, then by the film of embodiment by being layered on culture after wet heat sterilization Primary surface, and being cultivated under the conditions of 37 DEG C, interval is for 24 hours in culture period, 72h, 144h and 240h observe and calculate large intestine bar respectively The sterilizing rate of bacterium and staphylococcus aureus.

Preparation liquid preparation example 1-9

Under nitrogen protection, according in table 1 composition (type of each compound and in the concentration of preparation liquid it is such as listed, Wherein, concentration refers to that the net quality of each compound accounts for the percentage of preparation liquid total weight), by each component under specified requirements (condition is shown in Table 1) is stirred to dissolving, then vacuum defoamation obtains corresponding preparation liquid；In table 1：

PVDF is available from the Kynoar of Arkema's MG15 trades mark, and number-average molecular weight is 210,000；

PVP is available from the polyvinylpyrrolidone of the traditional Chinese medicines reagent Co., Ltd K30 trades mark, and number-average molecular weight is 30,000；

PEG20,000 is available from the polyethylene glycol of traditional Chinese medicines reagent Co., Ltd, and number-average molecular weight is 20,000；

PEG400 is available from the polyethylene glycol of traditional Chinese medicines reagent Co., Ltd, number-average molecular weight 400；

PEG600 is available from the polyethylene glycol of the traditional Chinese medicines reagent Co., Ltd trade mark, number-average molecular weight 600；

Polyethylene oxide is purchased from traditional Chinese medicines reagent Co., Ltd, and number-average molecular weight is 40,000.

PES is available from the polyether sulfone of traditional Chinese medicines reagent Co., Ltd, and number-average molecular weight is 100 000；

PAN is available from the polyacrylonitrile of traditional Chinese medicines reagent Co., Ltd, and number-average molecular weight is 80 000.

Preparation liquid prepares comparative example 1

According to the preparation process of preparation liquid B2, the difference is that, dopamine and glycerine are not used, and the amount of PVDF is increased To 22 weight %, the amount of PVP is increased into 12 weight %, to which preparation liquid DB1 be made.

Preparation liquid prepares comparative example 2

According to the preparation process of preparation liquid B2, the difference is that, dopamine and PVP are not used, and the amount of PVDF is increased to The amount of glycerine is increased to 12 weight % by 22 weight %, to which preparation liquid DB2 be made.

Table 1

Embodiment 1-1

The present embodiment is used to illustrate the antimicrobial form hollow-fibre membrane and preparation method thereof of the present invention.

(1) by 200 filament polyester filaments (fiber number is the solid long filament of 50D) and 5 filamentary silvers (fiber number 50D) Mixing immerse in the sodium hydroxide solution of 5 weight %, and 30min is activated at 60 DEG C, then by isolated filament It is cleaned with deionized water, and with the speed of 3000rpm centrifugation 30min to drying.

(2) filament of the activation obtained by step (1) in preparation liquid B1 is impregnated into 1min, and gained mixture is sent into It is woven in the braiding head of woven tube crochet, woven tube of the leaching after braiding containing preparation liquid, which will enter woven tube coater, to glue It is attached to preparation liquid extra around filament and scrapes and dash out, under the traction of friction pulley, squeezed with entering under the forward speed of 4m/min Go out nozzle to be coextruded.Then enter in 60 DEG C of coagulating bath (i.e. water), to obtain antimicrobial form hollow-fibre membrane.

(3) the antimicrobial form hollow-fibre membrane obtained by step (2) is impregnated into 12h to carry out at hydrophiling in 60 DEG C of water Reason；By treated, tunica fibrosa is cleaned with deionized water, and is dried for 24 hours at 30 DEG C.Thus antimicrobial form hollow-fibre membrane is obtained M1, SEM figure are as shown in Figure 1.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-2

According to the method described in embodiment 1-1, the difference is that：

Step (1)：It is (fine using 100 filament nylon fibers (fiber number is the solid long filament of 150D) and 10 filamentary silvers Degree is 150D)；Alkaline solution is the potassium hydroxide solution of 7.5 weight %, activation condition：Temperature is 50 DEG C, time 25min； Centrifugal condition is：Rotating speed 5000rpm, time 25min；

Step (2)：The filament of activation obtained by step (1) is impregnated into 2min in preparation liquid B2；Hauling speed is 3m/ min；

Step (3)：Hydrophilicity-imparting treatment condition：Temperature is 70 DEG C, time 12h.Thus antimicrobial form hollow-fibre membrane is obtained M2。

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-3

According to the method described in embodiment 1-1, the difference is that：

Step (1)：Filament uses 150 filament nylon fibers (fiber number is the solid long filament of 100D) and 8 filamentary silvers (fine Degree is 100D)；Alkaline solution is the sodium hydroxide solution of 10 weight %, activation condition：Temperature is 50 DEG C, time 30min；From Heart condition is：Rotating speed 5000rpm, time 25min；

Step (2)：The filament of activation obtained by step (1) is impregnated into 3min in preparation liquid B3；Hauling speed is 3m/ min；Coagulating bath is that weight ratio is 1：4 DMAc and H₂The mixture of O (temperature is 60 DEG C)；

Step (3)：Hydrophilicity-imparting treatment condition：Temperature is 60 DEG C, time 6h；Drying condition is 25 DEG C and dries for 24 hours.Thus Obtain antimicrobial form hollow-fibre membrane M3.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-4

According to the method described in embodiment 1-1, the difference is that：

Step (2)：Preparation liquid B1 is replaced using preparation liquid B4；

Thus antimicrobial form hollow-fibre membrane M4 is obtained.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-5

According to the method described in embodiment 1-1, the difference is that：

Step (1)：Filament uses 100 filament nylon fibers (fiber number is the solid long filament of 250D) and 10 filamentary silvers (fiber number 250D)；Alkaline solution is the sodium carbonate liquor of 8 weight %, activation condition：Temperature is 60 DEG C, time 15min；From Heart condition is：Rotating speed 10,000rpm, time 15min；

Step (2)：The filament of activation obtained by step (1) is impregnated into 5min in preparation liquid B5；Hauling speed is 1.5m/min；

Step (3)：Hydrophilicity-imparting treatment condition：Temperature is 60 DEG C, time 6h；Drying condition is 25 DEG C and dries for 24 hours.Thus Obtain antimicrobial form hollow-fibre membrane M5.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-6

According to the method described in embodiment 1-1, the difference is that：

Step (1)：Filament uses 80 filament nylon fibers (fiber number is the solid long filament of 300D) and 8 filamentary silvers (fine Degree is 300D)；Alkaline solution is the solution of potassium carbonate of 10 weight %, activation condition：Temperature is 60 DEG C, time 15min；Centrifugation Condition is：Rotating speed 10,000rpm, time 15min；

Step (2)：The filament of activation obtained by step (1) is impregnated into 3min in preparation liquid B1；Hauling speed is 3m/ min；The temperature of water as coagulating bath is 65 DEG C；

Step (3)：Drying condition is 25 DEG C and dries for 24 hours.Thus antimicrobial form hollow-fibre membrane M6 is obtained.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-7

According to the method described in embodiment 1-1, unlike, used in step (1) 200 glass fibers (fiber number for The solid long filament of 300D) replace filament polyester filament；

After each step, antimicrobial form hollow-fibre membrane M7 is thus obtained.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-8

According to the method described in embodiment 1-1, the difference is that：

Step (4)：The preparation liquid used is preparation liquid B6；

After each step, antimicrobial form hollow-fibre membrane M8 is thus obtained.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-9

According to the method described in embodiment 1-1, the difference is that：

Step (4)：The preparation liquid used is preparation liquid B7；

After each step, antimicrobial form hollow-fibre membrane M9 is thus obtained.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-10

According to the method described in embodiment 1-1, the difference is that：

Step (4)：The preparation liquid used is preparation liquid B8；

After each step, antimicrobial form hollow-fibre membrane M10 is thus obtained.

The properties of the film are as shown in tables 2 and 3.

Embodiment 1-11

According to the method described in embodiment 1-1, the difference is that：

Step (4)：The preparation liquid used is preparation liquid B9；

After each step, antimicrobial form hollow-fibre membrane M11 is thus obtained.

The properties of the film are as shown in tables 2 and 3.

Comparative example 1-1

According to the method described in embodiment 1-1, the difference is that：

Step (2)：The preparation liquid used is preparation liquid DB1；

After each step, antimicrobial form hollow-fibre membrane DM1 is thus obtained.

The properties of the film are as shown in tables 2 and 3.

Comparative example 1-2

According to the method described in embodiment 1-1, the difference is that：

Step (2)：The preparation liquid used is preparation liquid DB2；

After each step, antimicrobial form hollow-fibre membrane DM2 is thus obtained.

The properties of the film are as shown in tables 2 and 3.

Comparative example 1-3

According to the method described in embodiment 1-1, the difference is that, step (1) does not use filamentary silver, but directly washs long filament Synthetic fibre fiber carries out activation process；

After each step, hollow-fibre membrane DM3 is thus obtained.

The properties of the film are as shown in tables 2 and 3.

Table 2

Table 3

It can be seen that antimicrobial form hollow-fibre membrane using the present invention is big with water flux, cuts by the result of table 2 and 3 Stay rate high while more preferable to the bactericidal effect of Escherichia coli and Staphylococcus aureus.

The second class invention offer for the present invention is exemplified below：

Embodiment 2-1

1) the hollow woven tube of the polyester fiber of internal diameter 1.0mm, outer diameter 1.7mm is immersed in the sodium hydroxide solution of 5wt%, 30min is handled at a temperature of 50 DEG C, is then cleaned with deionized water, 5min is centrifuged with 3000 revs/min of speed, in 80 DEG C of temperature Degree drying.

2) the Tris buffer solutions for configuring pH 8.5, it is uniformly mixed with dopamine and polyethyleneimine, and DOPA is made Amine concentration is the modified solution of 4.0wt% and a concentration of 10wt% of polyethyleneimine；Treated woven tube is immersed in Primary coating is carried out in the modified solution, is handled 30min at a temperature of 60 DEG C, is cleaned with deionized water, centrifuge dripping.

3) treated woven tube is soaked in 2% CaCl₂Mineralising is carried out in solution, in (25 DEG C) processing of room temperature 8h, in braiding pipe surface growth nano particle (25.6 ± 3.6nm)；After deionized water cleaning, dried at a temperature of 60 DEG C.

4) under the conditions of nitrogen protection, Kynoar, additive, dopamine and solvent are blended, stirred at 80 DEG C For 24 hours, vacuum defoamation obtains casting solution, casting solution each component and its a concentration of as follows：

The number-average molecular weight of Kynoar is 2.1 × 10⁵, weight percent concentration 10%；

Additive is polyvinylpyrrolidone, number-average molecular weight 30000, weight percent concentration 8.0%；

The weight percent concentration of dopamine is 6%；

Solvent is n,N-dimethylacetamide, weight percent concentration 76%.

5) secondary coating is carried out to the woven tube after mineralising with casting solution, into 40 DEG C of coagulating baths, obtains gathering inclined fluorine Ethylene doughnut composite micro porous film, air themperature are 30 DEG C, relative humidity 75%, air section distance 10cm.

The coagulating bath is water.

6) polyvinylidene fluoride hollow fiber composite micro porous film is impregnated into 6h in the hot water and carries out hydrophilicity-imparting treatment, the water of hot water Temperature is 80 DEG C；It is then cleaned with deionized water, is dried for 24 hours at 30 DEG C.Obtain having the braiding tube enhancement type of high bond strength poly- Vinylidene hollow-fibre membrane.

Embodiment 2-2

1) the nylon fiber woven tube of internal diameter 1.0mm, outer diameter 1.7mm are immersed in the sodium hydroxide solution of 7.5wt%, 20min is handled at a temperature of 45 DEG C, is then cleaned with deionized water, 10min is centrifuged with 5000 revs/min of speed, in 80 DEG C of temperature Degree drying.

2) the Tris buffer solutions for configuring pH 8.5, will uniformly mix with dopamine and diethylenetriamine, and dopamine is made The modified solution of a concentration of 8.0wt% and a concentration of 15wt% of diethylenetriamine；Treated woven tube is immersed in institute It states and carries out primary coating in modified solution, handle 20min at a temperature of 70 DEG C, cleaned with deionized water, centrifuge dripping.

3) treated woven tube is soaked in the AgNO of 3wt%₃Mineralising is carried out in solution, at room temperature (25 DEG C) 7h is managed, in braiding pipe surface growth nano particle (16.4 ± 2.6nm)；After deionized water cleaning, dried at a temperature of 70 DEG C It is dry.

The number-average molecular weight of Kynoar is 2.1 × 10⁵, weight percent concentration 15%；

Additive is polyvinylpyrrolidone (PVP), number-average molecular weight 30000, weight percent concentration 5.5%；

The weight percent concentration of dopamine is 3.5%；

Solvent is n,N-dimethylacetamide, weight percent concentration 86%.

The coagulating bath is water.

6) polyvinylidene fluoride hollow fiber composite micro porous film is impregnated into 12h in the hot water and carries out hydrophilicity-imparting treatment, hot water Water temperature is 80 DEG C；It is then cleaned with deionized water, is dried for 24 hours at 30 DEG C.Obtain the braiding tube enhancement type with high bond strength Pvdf Microporous Hollow Fiber Membrane.

Embodiment 2-3

1) the hollow woven tube of the nylon fiber of internal diameter 1.0mm, outer diameter 1.7mm is immersed to the sodium hydroxide solution of 10wt% In, 15min is handled at a temperature of 50 DEG C, is then cleaned with deionized water, 10min is centrifuged with 8000 revs/min of speed, in 80 The drying of DEG C temperature.

2) the Tris buffer solutions for configuring pH 8.5, it is uniformly mixed with tannic acid and diethylenetriamine, and tannin is made Acid concentration is the modified solution of 5wt% and a concentration of 10wt% of diethylenetriamine；Treated woven tube is immersed in institute It states and carries out primary coating in modified solution, handle 40min at a temperature of 60 DEG C, cleaned with deionized water, centrifuge dripping.

3) treated woven tube is soaked in the FeCl of 5wt%₂Mineralising is carried out in solution, at room temperature (25 DEG C) 6h is managed, in braiding pipe surface growth nano particle (13.8 ± 2.2nm)；After deionized water cleaning, dried at a temperature of 60 DEG C It is dry.

4) under the conditions of nitrogen protection, Kynoar, PEG, tannic acid and n,N-dimethylacetamide are blended, 80 DEG C stirring 18h, vacuum defoamation obtain casting solution, casting solution each component and its a concentration of as follows：

The number-average molecular weight 20000 of PEG, weight percent concentration 4.5%；

The weight percent concentration of tannic acid is 4%；

The weight percent concentration of DMAC N,N' dimethyl acetamide is 81.5%.

The coagulating bath is water.

6) polyvinylidene fluoride hollow fiber composite micro porous film is impregnated into 10h in the hot water and carries out hydrophilicity-imparting treatment, hot water Water temperature is 70 DEG C；It is then cleaned with deionized water, in 40 DEG C of dry 18h.Obtain the braiding tube enhancement type with high bond strength Pvdf Microporous Hollow Fiber Membrane.

Embodiment 2-4

1) the hollow woven tube of the polyester fiber of internal diameter 1.0mm, outer diameter 1.7mm is immersed in the sodium hydroxide solution of 8wt%, 15min is handled at a temperature of 60 DEG C, is then cleaned with deionized water, 10min is centrifuged with 8000 revs/min of speed, in 80 DEG C Temperature is dried.

2) PBS buffer solutions are configured, it is uniformly mixed with tannic acid and polyethyleneimine, it is a concentration of that tannic acid is made The modified solution of 5wt% and a concentration of 12wt% of polyethyleneimine；It is molten that treated woven tube is immersed in the modification Primary coating is carried out in liquid, is handled 50min at a temperature of 60 DEG C, is cleaned with deionized water, centrifuge dripping.

3) treated woven tube is soaked in the CaCl of 3.5wt%₂Mineralising is carried out in solution, at room temperature (25 DEG C) 6h is handled, in braiding pipe surface growth nano particle (18.6 ± 2.6nm)；After deionized water cleaning, at a temperature of 80 DEG C Drying.

4) under the conditions of nitrogen protection, Kynoar, PVP, tannic acid and n,N-dimethylacetamide are blended, 80 DEG C stirring 18h, vacuum defoamation obtain casting solution, casting solution each component and its a concentration of as follows：

The number-average molecular weight of Kynoar is 2.1 × 10⁵, weight percent concentration 12%；

The number-average molecular weight 40000 of PVP, weight percent concentration 4%；

The weight percent concentration of tannic acid is 4%；

The weight percent concentration of DMAC N,N' dimethyl acetamide is 80%.

The coagulating bath is water.

6) polyvinylidene fluoride hollow fiber composite micro porous film is impregnated into 8h in the hot water and carries out hydrophilicity-imparting treatment, the water of hot water Temperature is 70 DEG C；It is then cleaned with deionized water, is dried for 24 hours at 40 DEG C.Obtain having the braiding tube enhancement type of high bond strength poly- Vinylidene hollow-fibre membrane.

Embodiment 2-5

1) the hollow woven tube of the polyester fiber of internal diameter 1.0mm, outer diameter 1.7mm is immersed in the sodium hydroxide solution of 8wt%, 25min is handled at a temperature of 60 DEG C, is then cleaned with deionized water, 15min is centrifuged with 5000 revs/min of speed, in 80 DEG C Temperature is dried.

2) PBS buffer solutions are configured, it is uniformly mixed with catechol and PEG, it is a concentration of that catechol is made 10wt% and the modified solution that PEG concentration is 15wt%；By treated woven tube be immersed in the modified solution into Row primary coating handles 50min at a temperature of 70 DEG C, is cleaned with deionized water, centrifuge dripping.

4) under the conditions of nitrogen protection, Kynoar, PEG, catechol and n,N-dimethylacetamide are blended, 80 DEG C of stirring 20h, vacuum defoamation obtain casting solution, casting solution each component and its a concentration of as follows：

The number-average molecular weight 20000 of PEG, weight percent concentration 5%；

The weight percent concentration of catechol is 5%；

The weight percent concentration of DMAC N,N' dimethyl acetamide is 80%.

The coagulating bath is water.

6) polyvinylidene fluoride hollow fiber composite micro porous film is impregnated into 10h in the hot water and carries out hydrophilicity-imparting treatment, hot water Water temperature is 70 DEG C；It is then cleaned with deionized water, is dried for 24 hours at 40 DEG C.Obtain the braiding tube enhancement type with high bond strength Pvdf Microporous Hollow Fiber Membrane.

Embodiment 2-6

1) the hollow woven tube of the glass fibre of internal diameter 1.0mm, outer diameter 1.7mm is immersed to the sodium hydroxide solution of 10wt% In, 15min is handled at a temperature of 70 DEG C, is then cleaned with deionized water, 15min is centrifuged with 5000 revs/min of speed, in 80 The drying of DEG C temperature.

2) PBS buffer solutions are configured, it is uniformly mixed with catechol and chitosan, it is a concentration of that catechol is made 12wt% and the modified solution that chitosan concentration is 12wt%；Treated woven tube is immersed in the modified solution Primary coating is carried out, 40min is handled at a temperature of 70 DEG C, is cleaned with deionized water, centrifuge dripping.

3) treated woven tube is soaked in the CuCl of 4.5wt%₂Mineralising is carried out in solution, at room temperature (25 DEG C) 8h is handled, in braiding pipe surface growth nano particle (17.2 ± 3.7nm)；After deionized water cleaning, at a temperature of 80 DEG C Drying.

4) under the conditions of nitrogen protection, Kynoar, PVP, catechol and n,N-dimethylacetamide are blended, 80 DEG C of stirring 18h, vacuum defoamation obtain casting solution, casting solution each component and its a concentration of as follows：

The number-average molecular weight 30000 of PVP, weight percent concentration 6%；

The weight percent concentration of catechol is 5.5%；

The weight percent concentration of DMAC N,N' dimethyl acetamide is 78.5%.

The coagulating bath is water.

Comparative example 2-1

2) under the conditions of nitrogen protection, Kynoar, additive, dopamine and solvent are blended, stirred at 80 DEG C For 24 hours, vacuum defoamation obtains casting solution, casting solution each component and its a concentration of as follows：

The weight percent concentration of dopamine is 6%；

Solvent is n,N-dimethylacetamide, weight percent concentration 76%.

3) secondary coating is carried out to woven tube with casting solution, into 40 DEG C of coagulating baths, it is hollow obtains Kynoar Fiber composite microporous barrier, air themperature are 30 DEG C, relative humidity 75%, air section distance 10cm.

The coagulating bath is water.

4) polyvinylidene fluoride hollow fiber composite micro porous film is impregnated into 6h in the hot water and carries out hydrophilicity-imparting treatment, the water of hot water Temperature is 80 DEG C；It is then cleaned with deionized water, is dried for 24 hours at 30 DEG C.Obtain having the braiding tube enhancement type of high bond strength poly- Vinylidene hollow-fibre membrane.

Doughnut tunica fibrosa prepared by embodiment 2-1 to 2-6 and comparative example 2-1 is subjected to following performance test：Water Flux is measured using the outer press filtering device of dead end, that is, then the present 0.15MPa precompressed 30min of wet film after cleaning exists 0.1MPa measures its external pressure water flux；It is subsequently passed BSA solution, measures rejection, flux recovery rate is measured after water cleans；It compiles The interface bond strength for knitting pipe and separating layer is measured using water kickback pressure；The water contact angle of dry film is surveyed by contact angle measurement It is fixed；Dry film surface and fracture morphology pass through field emission microscopy observation.

Test result is as shown in table 4.

Table 4：The structure and performance parameter of PVDF hollow-fibre membranes：

Third class invention offer for the present invention is exemplified below：

Embodiment 3-1

1, the fibre bundle being made of 200 0.5 Denier dacron threads and the fibre bundle for replacing 4 nano silver wires are existed In the sodium hydroxide solution of 5wt%, 30min is handled at a temperature of 60 DEG C, is then cleaned with deionized water, with 3000 revs/min Speed centrifuge dripping 30min.

2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, polyethylene glycol 400, polyethylene pyrrole Pyrrolidone presses 15:70:10:5 weight ratio stirs 12 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 24 hours obtain casting film Liquid.

3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure₂O exists as core liquid Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley, Nozzle is squeezed out to enter under the forward speed of 4m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die Go out, immerses 60 DEG C of H₂It is separated in O coagulating baths, obtains argentiferous hollow-fibre membrane.

4, obtained hollow-fibre membrane is impregnated 12 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 30 DEG C, just obtained having both after dry high mechanical properties and The hollow fiber ultrafiltration membrane of anti-microbial property.

Embodiment 3-2

1, the fibre bundle being made of 150 0.7 Denier glass fibers and the fibre bundle for replacing 6 nano silver wires are existed In the sodium hydroxide solution of 10wt%, 25min is handled at a temperature of 50 DEG C, is then cleaned with deionized water, with 5000 revs/min Speed centrifuge dripping 25min.

2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, glycerine, polyvinyl alcohol 30000 By 15:70:10:5 weight ratio stirs 18 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 18 hours obtain casting solution.

3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure₂O exists as core liquid Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley, Nozzle is squeezed out to enter under the forward speed of 3m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die Go out, immerses 60 DEG C of H₂It is separated in O coagulating baths, obtains argentiferous hollow-fibre membrane.

4, obtained hollow-fibre membrane is impregnated 12 hours in 70 DEG C of hot water, after carrying out hydrophiling and fenestra sizing Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 30 DEG C, just obtained having both after dry high mechanical properties and The hollow fiber ultrafiltration membrane of anti-microbial property.

Embodiment 3-3

1, the fibre bundle being made of 200 0.5 Denier nylon fiber silks and the fibre bundle for replacing 8 nano silver wires are existed In the sodium hydroxide solution of 10wt%, 30min is handled at a temperature of 50 DEG C, is then cleaned with deionized water, with 5000 revs/min Speed centrifuge dripping 25min.

2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, Macrogol 600, polyvinyl alcohol 30000 press 18:68:9:5 weight ratio stirs 24 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 18 hours obtain casting film Liquid.

3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure₂O exists as core liquid Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley, Nozzle is squeezed out to enter under the forward speed of 3m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die Go out, immerses 60 DEG C of n,N-dimethylacetamide/H₂O (weight ratios 1:4) it is separated in coagulating bath, obtains the hollow fibre of argentiferous Tie up film.

4, obtained hollow-fibre membrane is impregnated 6 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 25 DEG C, just obtained having both after dry high mechanical properties and The hollow fiber ultrafiltration membrane of anti-microbial property.

Embodiment 3-4

1, by the fibre bundle of 10 nano silver wires of the fibre bundle being made of 300 0.5 Denier nylon fiber silks and replacement In the sodium hydroxide solution of 15wt%, handle 30min at a temperature of 60 DEG C, then cleaned with deionized water, with 10000 turns/ The speed centrifuge dripping 15min of minute.

2, by Kynoar (molecular weight 430000), DMAC N,N' dimethyl acetamide, glycerine, PEG 20000 By 20:64:10:6 weight ratio stirs 18 hours at a temperature of 90 DEG C, and filtering, vacuum defoamation 18 hours obtain casting solution.

3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure₂O exists as core liquid Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley, Nozzle is squeezed out to enter under the forward speed of 1.5m/min.Casting solution, core liquid, fiber braided tube are total to by extrusion die It squeezes out, immerses 60 DEG C of n,N-dimethylacetamide/H₂O (weight ratios 1:6) it is separated in coagulating bath, it is hollow to obtain argentiferous Tunica fibrosa.

4, obtained hollow-fibre membrane is impregnated 6 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing Reason；Hollow-fibre membrane after hydrophilicity-imparting treatment is 24 hours dry at 2 DEG C, it has just obtained having both high mechanical properties after dry and resist The hollow fiber ultrafiltration membrane of bacterium performance.

Embodiment 3-5

1, the fibre bundle being made of 300 0.5 Denier polyester fiber silks and the fibre bundle for replacing 8 nano silver wires are existed In the sodium hydroxide solution of 15wt%, 15min is handled at a temperature of 60 DEG C, is then cleaned with deionized water, with 10000 revs/min The speed centrifuge dripping 15min of clock.

2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, glycerine, PEG 20000 By 20:64:10:6 weight ratio stirs 18 hours at a temperature of 90 DEG C, and filtering, vacuum defoamation 18 hours obtain casting solution.

3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure₂O exists as core liquid Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley, Nozzle is squeezed out to enter under the forward speed of 1.5m/min.Casting solution, core liquid, fiber braided tube are total to by extrusion die It squeezes out, immerses in 60 DEG C of water coagulating bath and be separated, obtain argentiferous hollow-fibre membrane.

Embodiment 3-6

1, the fibre bundle being made of 150 0.5 Denier polyester fiber silks and the fibre bundle for replacing 6 nano silver wires are existed In the sodium hydroxide solution of 15wt%, 15min is handled at a temperature of 60 DEG C, is then cleaned with deionized water, with 10000 revs/min The speed centrifuge dripping 15min of clock.

2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, glycerine, PEG 20000 By 15:71:8.5:5.5 weight ratio stirs 24 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 12 hours obtain casting solution.

3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure₂O exists as core liquid Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley, Nozzle is squeezed out to enter under the forward speed of 3m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die Go out, immerses in 60 DEG C of water coagulating bath and be separated, obtain argentiferous hollow-fibre membrane.

4, obtained hollow-fibre membrane is impregnated 12 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 25 DEG C, just obtained having both after dry high mechanical properties and The hollow fiber ultrafiltration membrane of anti-microbial property.

Comparative example 3-1

1, the fibre bundle being made of 200 0.5 Denier dacron threads is immersed in the sodium hydroxide solution of 5wt%, 60 30min is handled at a temperature of DEG C, is then cleaned with deionized water, with 3000 revs/min of speed centrifuge dripping 30min.

3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure₂O exists as core liquid Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley, Nozzle is squeezed out to enter under the forward speed of 4m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die Go out, immerses 60 DEG C of H₂It is separated in O coagulating baths, obtains hollow-fibre membrane.

4, obtained hollow-fibre membrane is impregnated 12 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing Reason；Hollow-fibre membrane after hydrophilicity-imparting treatment is 24 hours dry at 30 DEG C, just obtain hollow fiber ultrafiltration membrane after dry.

Embodiment 3-1 to 3-6 and comparative example the 3-1 hollow fiber ultrafiltration membrane being prepared are tested for the property.

Test condition is as follows：Water flux is measured using the outer press filtering device of the homemade dead end in laboratory, that is, after cleaning The present 0.15MPa precompressed 30min of wet film, then measure its external pressure water flux in 0.1MPa；It is subsequently passed BSA (molecular weight 6700) solution measures rejection, and flux recovery rate is measured after water cleans；The interface bond strength of woven tube and separating layer is adopted It is measured with water kickback pressure；The water contact angle of dry film is measured by the contact angle measurement of OCA20 (Dataphysics, Germany)； Dry film surface and fracture morphology are observed by field emission scanning electron microscope SIRION-100 (FEI, Finland).Institute in antibacterial tests The model bacterium of selection is Escherichia coli and staphylococcus aureus.

The water flux of prepared fibrage enhancing hollow fiber ultrafiltration membrane, rejection, backwash membrane fracture pressure, contact Angle, fracture strength, Escherichia coli sterilizing rate, staphylococcus aureus sterilizing rate are shown in Table 5.

Table 5

The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to Protection scope of the present invention.

Claims

1. a kind of preparation method of antimicrobial form hollow-fibre membrane, which is characterized in that this method includes：

(2) filament by the activation is mixed with preparation liquid, and gained mixture is woven, woven hollow fiber is obtained Pipe；

Wherein, the preparation liquid contains film forming polymer, pore-foaming agent and additive A；The additive A is that polyalcohol sum number is divided equally Son amount is less than one or more in 1,000 polyvalent alcohol.

2. it is described to be mixed in the filament of filamentary silver according to the method described in claim 1, wherein, relative to 100 fibers The quantity of silk, the filamentary silver is 2-50 roots；

Preferably, the fiber number of the filamentary silver is 10-500D, preferably 50-300D, more preferably 100-200D；

Preferably, the filament for being mixed with filamentary silver is made of the filamentary silver and film forming filament, and the film forming filament is poly- Ester fiber, Fypro, polyolefine fiber, polyester fiber, polyurethane fiber, polyvinylidene fluoride, polysulfone fibre and glass It is one or more in glass fiber, preferably polyester fiber and/or Fypro；

Preferably, the filametntary fiber number of film forming is 5-10D；

Preferably, the filametntary fiber number of film forming is 10-500D, preferably 50-300D, more preferably 100-200D.

3. method according to claim 1 or 2, wherein in step (1), the alkali compounds in the alkaline solution is One kind or more in alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate and ammonia Kind, preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, carbon It is one or more in potassium hydrogen phthalate and ammonia；

Preferably, the content of the alkali compounds in the alkaline solution is 5-15 weight %.

4. method according to claim 1 or 2, wherein in step (2), in the preparation liquid, the film forming polymer, The weight ratio of pore-foaming agent and additive A is 100：15-70：20-150, preferably 100：20-60：30-100；

Preferably, the film forming polymer is one or more in Kynoar, polyether sulfone and polyacrylonitrile；

Preferably, the pore-foaming agent is polyvinylpyrrolidone, the polyethylene glycol of number-average molecular weight 1,000 or more, polycyclic oxygen It is one or more in ethane, polyvinyl alcohol, polymethyl methacrylate and polyvinyl acetate, more preferably number-average molecular weight For 3,000-50,000 polyvinylpyrrolidones, the polyethylene glycol of number-average molecular weight 1,000-10,000, number-average molecular weight 10, The polyethylene oxide of 000-60,000, the polyvinyl alcohol of number-average molecular weight 8,000-50,000 and molecular weight 11,000-85,000 Polymethyl methacrylate in it is one or more；

Preferably, the additive A is propylene glycol, glycerine, triethylene glycol, number-average molecular weight are 200-800 polyethylene glycol, number One in polypropylene glycol, polyvinylpyrrolidone, polyvinyl butyral and polyvinyl acetate that average molecular weight is 200-800 Kind is a variety of；

Preferably, the solvent in the preparation liquid is N, N '-dimethyl formamide, N, N '-dimethyl acetamide, N- methylpyrroles One or more in alkanone, triethyl phosphate, sulfolane, dimethyl sulfone and benzophenone, the film forming polymer is molten with this The weight ratio of agent is 1：2-8.

5. method according to claim 1 or 4, wherein the preparation liquid also contains polyphenol compound, the Polyphenols Compound is one or more in formula (1) compound represented, tannic acid, formula (2) compound represented and green-tea extract；

Wherein, formula (1)Formula (2)

R¹-R⁶In at least 2 be OH, it is remaining to be each independently H, halogen ,-L-COOM ,-L-SO₃M、-L-NH₂、-L-OH、 The alkylthio group of the alkyl of C1-C6, the alkoxy of C1-C6 or C1-C6；R⁷-R¹⁰And R¹³-R¹⁷In at least 2 be OH, it is remaining R⁷-R¹⁰And R¹³-R¹⁷And R¹¹-R¹²It is each independently H, halogen ,-L-COOM ,-L-SO₃M、-L-NH₂,-L-OH, C1-C6 The alkylthio group of alkyl, the alkoxy of C1-C6 or C1-C6；Each L is each independently selected from the alkylidene of C0-C6；Each M is respectively It independently is H and alkali metal element；

Preferably, R¹-R⁶In at least 2 be OH, it is remaining to be each independently H, halogen ,-L-COOM ,-L-SO₃M、-L- NH₂,-L-OH, the alkyl of C1-C4, the alkoxy of C1-C4 or C1-C4 alkylthio group；R⁷-R¹⁰And R¹³-R¹⁷In at least 2 be OH, remaining R⁷-R¹⁰And R¹³-R¹⁷And R¹¹-R¹²It is each independently H, halogen ,-L-COOM ,-L-SO₃M、-L-NH₂、-L- The alkylthio group of the alkyl of OH, C1-C4, the alkoxy of C1-C4 or C1-C4；Each L is each independently selected from the alkylidene of C0-C4； Each M is each independently H, Na and K；

It is highly preferred that R¹-R⁶In at least 2 be OH, it is remaining to be each independently H, F, Cl, Br ,-COOM ,-CH₂- COOM、-CH₂CH₂-COOM、-CH₂CH₂CH₂-COOM、-CH(CH₃)CH₂-COOM、-CH₂CH(CH₃)-COOM、- CH₂CH₂CH₂CH₂-COOM、-SO₃M、-CH₂-SO₃M、-CH₂CH₂-SO₃M、-CH₂CH₂CH₂-SO₃M、-CH(CH₃)CH₂-SO₃M、- CH₂CH(CH₃)-SO₃M、-CH₂CH₂CH₂CH₂-SO₃M、-NH₂、-CH₂-NH₂、-CH₂CH₂-NH₂、-CH₂CH₂CH₂-NH₂、-CH (CH₃)CH₂-NH₂、-CH₂CH(CH₃)-NH₂、-CH₂CH₂CH₂CH₂-NH₂、-OH、-CH₂-OH、-CH₂CH₂-OH、-CH₂CH₂CH₂- OH、-CH(CH₃)CH₂-OH、-CH₂CH(CH₃)-OH、-CH₂CH₂CH₂CH₂- OH, methyl, ethyl, n-propyl, isopropyl, positive fourth It is base, isobutyl group, sec-butyl, tertiary butyl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, secondary Butoxy, tert-butoxy, methyl mercapto, ethylmercapto group, positive rosickyite base, isopropyisulfanyl, positive butylthio, isobutylthio, secondary butylthio or Tertiary butylthio；

Preferably, in the preparation liquid, the weight ratio of the film forming polymer and polyphenol compound is 100：10-50, preferably It is 100：15-40.

6. according to the method described in claim 5, wherein,

Formula (1) compound represented is selected from following formula compound represented：

Formula (2) compound represented is selected from following formula compound represented：

7. according to the method described in any one of claim 1-6, wherein in step (1), the condition packet of the activation process It includes：Temperature is 30-80 DEG C, time 10-50min.

8. method according to any one of claims 1-7, wherein this method further includes：After step (2), by institute It obtains woven hollow fiber pipe and carries out solidification and washing process, wherein the temperature of the solidification and washing process is 30-80 DEG C.

9. according to the method described in any one of claim 1-8, wherein step (3) further includes in the antimicrobial form by gained Empty fiber membrane carries out hydrophilicity-imparting treatment, and the condition of the hydrophilic treated includes：Using 40-90 DEG C of hot water, 2-24h is impregnated.

10. the antimicrobial form hollow-fibre membrane made from the method described in any one of claim 1-9.

11. including the membrane bioreactor of antimicrobial form hollow-fibre membrane according to any one of claims 10.

12. application of the antimicrobial form hollow-fibre membrane according to any one of claims 10 in UF membrane.