CN105617876A - Sustained-release type antibacterial double-layer hollow fiber membrane and preparation method thereof - Google Patents
Sustained-release type antibacterial double-layer hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN105617876A CN105617876A CN201410623483.0A CN201410623483A CN105617876A CN 105617876 A CN105617876 A CN 105617876A CN 201410623483 A CN201410623483 A CN 201410623483A CN 105617876 A CN105617876 A CN 105617876A
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Abstract
The present invention discloses a sustained-release type antibacterial double-layer hollow fiber membrane and a preparation method thereof, wherein the sustained-release type antibacterial double-layer hollow fiber membrane comprises an outer layer containing a metal silver supporting molecular sieve, and a porous inner layer, the outer layer comprises a mixture of a polymer and a metal silver supporting molecular sieve, and the inner layer comprises a porous polymer having a mechanical support effect. According to the present invention, the sustained-release type antibacterial double-layer hollow fiber membrane prepared by using the method has effects of sustained silver ion release, lasting antibacterial effect maintaining, and antibacterial film service life prolonging.
Description
Technical field
The invention belongs to separation film field, in particular it relates to a kind of method preparing slowly released type antibiotic double-layer hollow fiber film by triple channel spinning head coextrusion one-step shaping method.
Background technology
Compared with the separation process such as traditional rectification, evaporation, extraction, adopt embrane method carry out water process have that operating condition gentleness, floor space be little, separation process is without advantages such as phase transformations. Occurring in that first double-layer hollow fiber composite membrane in phase late 1970s, since then, the research of double-layer hollow fiber film starts flourish with preparation. Triple channel coextrusion one-step shaping method is to prepare the main method of double-layer hollow fiber film, refers to that internal layer casting solution, outer layer casting solution and core liquid three extrude simultaneously from three-channel spinning head, through solidification and solidification, an one-step film forming. Adopt double-layer hollow fiber film prepared by this method except have high-specific surface area, self supporting structure, can the advantage such as under high pressure operation, also there is the advantage of oneself uniqueness: 1) save the expense of performance function material; 2) fragility can be chosen, but selectivity or the high material of permeability are as functional layer; 3) step forms double-layer hollow fiber film, it is to avoid functional coat is coated in the secondary operation on single layer hollow fibrous membrane, and preparation process is more economical compared with other kinds of composite membrane, more optimize.
Although having above advantage, but using double-layer hollow fiber film to carry out, in the process of water process, still inevitably producing fouling membrane, so that performance and used life reduces. For membrane pollution problem, current most common method of modifying is to improve its hydrophilicity, for instance adopt blended hydrophilic inorganic particle, hydrophilic polymer, surface grafting hydrophilic polymer, surface-coated hydrophilic polymer etc. In Chinese invention patent CN102179192A and CN101439271A, the former is prepared for fluorine-containing amphipathic material modified preparing pollution-resistant membrane as filler, the latter is then to improve the antifouling property of film at film surface grafting hydrophilic macromolecule chain, but these process can not reach to kill the effect of antibacterial. And in numerous influence factors causing fouling membrane, bacterial micro-organism is a very important aspect. If the film of preparation can suppress the growth of antibacterial, that just can reduce the microorganisms such as the antibacterial absorption on film surface in the process used, and reduces fouling membrane. Chinese patent CN102863721A and CN1958136A adopts silver molecular sieve as antibacterial to prepare antibacterial hollow-fibre membrane, reach to kill antibacterial and reduce the purpose of fouling membrane, but do not mention the slow releasing function of antibacterial in antibacterial film and the persistence of antibacterial effect in the patent.
Therefore, in this area in the urgent need to develop a kind of have slow-release function, can the antibacterial double-layer hollow fiber film of long duration.
Summary of the invention
It is an object of the invention to provide a kind of slowly released type antibiotic double-layer hollow fiber film and preparation method thereof.
A first aspect of the present invention provides a kind of slowly released type antibiotic double-layer hollow fiber film, and described fibrous membrane is cannulated structure, and described fibrous membrane includes:
(1) outer layer;
(2) internal layer being combined with each other with outer layer;
Wherein, described outer layer includes the first polymer and the carried metal silver molecular sieve being doped in described first polymer; Described internal layer includes second polymer with loose structure.
In another preference, the content A of carried metal silver molecular sieve in described internal layerinWith the content A of carried metal silver molecular sieve in outer layeroutRatio be 0-0.2:1, it is preferred that 0-0.1:1, is more preferably 0-0.02:1.
In another preference, described internal layer does not contain carried metal silver molecular sieve.
In another preference, described internal layer is loose structure (having the macropore that aperture is 100-1200 micron).
In another preference, described double-layer hollow fiber film, its external diameter is 1100��1500 microns, and/or internal diameter is 500��700 microns.
In another preference, described double-layer hollow fiber film, the material of its first polymer is selected from lower group: Kynoar, SPSF, sulfonated polyether sulfone, polyacrylonitrile, polyimides, polylactic acid, polyether sulfone, polysulfones, cellulose acetate, or its combination.
In another preference, described first polymeric material is Kynoar.
In another preference, described double-layer hollow fiber film, the material of its second polymer is selected from lower group: Kynoar, polyacrylonitrile, polyimides, polylactic acid, polyether sulfone, polysulfones, cellulose acetate, or its compositions.
In another preference, the second polymeric material is Kynoar.
In another preference, described first, second polymer contains the polymeric material that at least two is different respectively.
In another preference, described double-layer hollow fiber film, its internal layer thickness is 100��500 microns, and/or outer layer thickness is 40��120 microns.
In another preference, the thickness ratio of ectonexine ranges for 1:5-5:1, it is preferable that for 3:1-2:1.
In another preference, described double-layer hollow fiber film outer layer comprises the carried metal silver molecular sieve accounting for outer layer the first polymer 2.5%��62.5wt%, and wherein silver carrying amount is 2��10wt% of carried metal silver molecular sieve.
In another preference, the pore diameter range of described double-layer hollow fiber its outer surface of film is 30��70 nanometers.
In another preference, described double-layer hollow fiber film pure water flux is 400��800L/ (m under the pressure of 0.1MPa2��h-1)��
A second aspect of the present invention provides a kind of method preparing slowly released type antibiotic double-layer hollow fiber film as described in the first aspect of the invention, said method comprising the steps of:
(1) internal layer casting solution and outer layer casting solution are provided;
Wherein, described outer layer casting solution contains the first polymer, carried metal silver molecular sieve, porogen, solvent; With
Described internal layer casting solution contains the loose structure of the second polymer, porogen, solvent;
(2) coextrusion one-step shaping method is adopted to prepare double-layer hollow fiber film.
In another preference, it it is 40��80 DEG C for preparing the whipping temp of internal layer casting solution.
In another preference, the mass percent of each material for preparing internal layer casting solution is: polymeric material 12��25%, porogen 2��8%, solvent 67��86%.
In another preference, the polymeric material for preparing internal layer casting solution is selected from lower group: Kynoar, polyacrylonitrile, polyimides, polylactic acid, polyether sulfone, polysulfones, cellulose acetate, or its combination.
In another preference, the porogen for preparing internal layer and outer layer casting solution is each independently selected from lower group: polyvinylpyrrolidone, Polyethylene Glycol, polyoxyethylene, or its combination.
In another preference, the solvent for preparing internal layer and outer layer casting solution is each independently selected from the mixture of one or any two kinds of lower group: trimethyl phosphate, triethyl phosphate, hexamethyl phosphoramide, tetramethylurea, dimethylformamide, dimethyl acetylamide, methyl pyrrolidone, dimethyl sulfoxide, oxolane.
In another preference, the mass percent of each material for preparing outer layer casting solution is: polymeric material 8��20%, porogen 3��10%, carried metal silver molecular sieve 0.5��5%, solvent 65��88.5%.
In another preference, the polymeric material for preparing outer layer casting solution is selected from lower group: Kynoar, SPSF, sulfonated polyether sulfone, polyacrylonitrile, polyimides, polylactic acid, polyether sulfone, polysulfones, cellulose acetate, or its combination.
In another preference, the rate of extrusion of described internal layer casting solution is 1��20 ml/min;
In another preference, the rate of extrusion of described outer layer casting solution is 0.8��16 ml/min;
In another preference, the rate of extrusion of described core liquid is 1��25 ml/min.
In another preference, the method also includes providing carried metal silver molecular sieve, and the preparation of described carried metal silver molecular sieve comprises the following steps:
I () utilizes molecular sieve and silver ion solution, prepare silver molecular sieve;
In another preference, molecular sieve type is selected from lower group: 3A, 4A, 5A, 13X, 10X, Y type and ZSM-5.
In another preference, molecular sieve mean diameter is not more than 1 micron.
In another preference, the solution of silver ion used is AgNO3Solution.
In another preference, described AgNO3Solution concentration is 0.1��0.5mol/L.
In another preference, add 5��20 milliliters of AgNO by every mole sieve3The ratio hybrid reaction of solution.
In another preference, molecular sieve and AgNO3Solution stirring reaction temperature is 40��80 DEG C; Mixing time is 4��8 hours.
In another preference, reducing agent used is selected from lower group: formaldehyde, glucose, sodium borohydride, hydrazine hydrate, citric acid, or its combination.
In another preference, reductant solution concentration is 0.2��1mol/L.
(ii) utilize reducing agent and silver molecular sieve, prepare carried metal silver molecular sieve.
In another preference, gained silver molecular sieve ultrasonic disperse water in deionization, stirs 0.5��2 hour at 30��60 DEG C, regulates pH to 8��10, continue stirring 0.5��2 hour.
In another preference, gained silver molecular sieve stirs and reacts for 1��4 hour after adding reducing agent.
A third aspect of the present invention provides a kind of goods, and described goods contain slowly released type antibiotic double-layer hollow fiber film as described in the first aspect of the invention.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus constituting new or preferred technical scheme. As space is limited, tired no longer one by one state at this.
Accompanying drawing explanation
Fig. 1 shows the outer surface of the film of the molecular sieve of the carried metal silver in one embodiment of the invention.
Fig. 2 shows the outer surface of common silver molecular sieve.
Fig. 3 shows the XRD figure of pure molecular sieve (zeolites), silver molecular sieve (Z-Ag+) and carried metal silver molecular sieve (Z-Ag).
The situation that three occurs at the characteristic peak of elemental silver has obvious difference, in figure 4 dashed region in the right be elemental silver characteristic peak (38.1 ��, 44.3 ��, 64.4 ��, 77.5 ��), only Z-Ag occurs in that these peaks, but compares with zeolites, the characteristic peak of molecular sieve (15.7 ��, 23.7 ��, 27.2 �� and 31.5 ��) all occur in that in 4, left side dashed region, simply the intensity at each peak is different, and this is that the impact by silver ion and elemental silver causes.
Detailed description of the invention
The present inventor is through research extensive and deep for a long time, by screening in a large number and testing, has prepared a kind of novel slowly released type antibiotic double-layer hollow fiber film first. Carried metal silver molecular sieve is loaded into the outer layer of hollow-fibre membrane by inventor, prepared fibrous membrane can slow releasing silver ion, reach lasting anti-microbial property and anti-bacterial attachment performance, reduce by bacterial fouling membrane, extend the service life of film. This preparation method is workable, controllability good, be prone to industrialized production. Complete the present invention on this basis.
Term
As used herein, term " slowly released type antibiotic double-layer hollow fiber film ", " sustained-release antibacterial film ", " anti-bacterial fibre film ", " antibacterial film ", " sustained-release antibacterial film of the present invention ", " sustained-release antibacterial fibrous membrane of the present invention ", " antibacterial film of the present invention " " duplicature of the present invention " " duplicature " etc. are used interchangeably, refer both to comprise open support internal layer and carried metal silver ion molecular sieve outer layer, there is the double-layer hollow fiber film of slowly released type antibiotic effect. Specifically, " the slowly released type antibiotic double-layer hollow fiber film " described in first aspect present invention is referred to.
The anti-microbial property evaluation methodology of fibrous membrane
Adopt coated plate counting method, with escherichia coli for object, have studied brand-new standby or in water, deposit the antibacterial effect of fibrous membrane of certain time. Concrete operating procedure is as follows: taking 40mL concentration is 1x106The bacterial solution of individual thalline/milliliter, joining in the conical flask containing a certain amount of fibrous membrane after sterilizing, matched group is added without described fibrous membrane, at 37 DEG C, the water bath with thermostatic control agitator of 100 revs/min is cultivated 1 hour, then above-mentioned bacterial solution is diluted different multiples (103��104��105Times) be coated on plating medium, 37 DEG C of calorstats are cultivated 24 hours, carries out colony counting.
The major advantage of the present invention has:
The invention provides a kind of slowly released type antibiotic double-layer hollow fiber film, described double layer fibre film can slow releasing silver ion, reach lasting anti-microbial property and anti-bacterial attachment performance, reduce by bacterial fouling membrane, extend the service life of film. This preparation method is workable, controllability good, be prone to industrialized production.
Below in conjunction with specific embodiment, the present invention is expanded on further. Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention. The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition, or according to manufacturer it is proposed that condition. Unless otherwise indicated, otherwise percentage ratio and number are percentage by weight and parts by weight.
Embodiment 1
A kind of preparation (1) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.1mol/LAgNO by the Y type molecular sieve of 0.5kg and 2.5L concentration3Solution mixes, and is stirred, makes Y type molecular sieve and AgNO at 40 DEG C3Solution occur sufficient ion-exchange reactions, reaction 8h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain Y type silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 0.5 hour at 40 DEG C, regulate pH to 8, continuing stirring 0.5 hour, the formalin adding 0.2mol/L continues stirring 1 hour, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of Y type molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
12kg Kynoar and 2kg Polyethylene Glycol are joined in 86kg trimethyl phosphate, stirs at 60 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
8kg polyimides, 0.5kg carried metal silver molecular sieve, 3kg polyvinylpyrrolidone order are joined in 88.5kg hexamethyl phosphoramide, stirs at 60 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 40 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 20 DEG C, extrudes with the rate of extrusion of 1 ml/min, 0.8 ml/min, 1 ml/min respectively. After casting solution sprays from spinneret exits, it is directly entered tank to solidify, form double-layer hollow fiber film, finally it is collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water, within first 3 days, changing a water every 24 hours, changed a water every 7 days after 3 days, following example are all identical.
After tested, colibacillary antibiotic rate is 91% (testing after placing 3 days, following example are all identical) by prepared slowly released type antibiotic double-layer hollow fiber film.
Embodiment 2
A kind of preparation (2) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.15mol/LAgNO by the 3A molecular sieve of 1kg and 7L concentration3Solution mixes, and is stirred, makes 3A molecular sieve and AgNO at 50 DEG C3Solution occur sufficient ion-exchange reactions, reaction 4h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain 3A silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 4 hours at 40 DEG C, regulate pH to 8.5, continuing stirring 1 hour, the glucose solution adding 0.25mol/L continues stirring 1 hour, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of 3A molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
15kg polyacrylonitrile and 3kg polyvinylpyrrolidone are joined in 82kg tetramethylurea, stirs at 70 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
10kg polylactic acid, 1kg carried metal silver molecular sieve sieve, 4kg polyoxyethylene order are joined in 85kg oxolane, stirs at 80 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 70 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 30 DEG C, extrudes with the rate of extrusion of 5 ml/min, 4 ml/min, 7 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 5 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, it is 93% to colibacillary antibiotic rate.
Embodiment 3
A kind of preparation (3) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.3mol/LAgNO by the 4A molecular sieve of 2kg and 15L concentration3Solution mixes, and is stirred, makes 4A molecular sieve and AgNO at 60 DEG C3Solution occur sufficient ion-exchange reactions, reaction 5h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain 4A silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 2 hours at 50 DEG C, regulate pH to 9, continuing stirring 1 hour, the sodium borohydride solution adding 0.4mol/L continues stirring 1 hour, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of 4A molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
18kg polyether sulfone and 4kg polyvinylpyrrolidone are joined in 78kg dimethyl acetylamide, stirs at 70 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
12kg cellulose acetate, 2kg carried metal silver molecular sieve, 5kg Polyethylene Glycol order are joined in 88.5kg tetramethylurea, stirs at 70 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 80 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 50 DEG C, extrudes with the rate of extrusion of 10 ml/min, 9 ml/min, 12 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 10 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, it is 95% to colibacillary antibiotic rate.
Embodiment 4
A kind of preparation (4) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.2mol/LAgNO by the 5A molecular sieve of 3kg and 20L concentration3Solution mixes, and is stirred, makes 5A molecular sieve and AgNO at 70 DEG C3Solution occur sufficient ion-exchange reactions, reaction 8h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain 5A silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 2 hours at 60 DEG C, regulate pH to 9, continuing stirring 2 hours, the citric acid solution adding 0.5mol/L continues stirring 4 hours, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of 5A molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
16kg polyimides and 3kg Polyethylene Glycol are joined in 81kg dimethyl sulfoxide, stirs at 80 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
15kg SPSF, 3kg carried metal silver molecular sieve, 5kg polyoxyethylene order are joined in 77kg methyl pyrrolidone, stirs at 60 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 70 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 40 DEG C, extrudes with the rate of extrusion of 15 ml/min, 14 ml/min, 18 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 15 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, colibacillary antibiotic rate is 94% by prepared slowly released type antibiotic double-layer hollow fiber film.
Embodiment 5
A kind of preparation (5) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.4mol/LAgNO by the 13X type molecular sieve of 4kg and 40L concentration3Solution mixes, and is stirred, makes 13X type molecular sieve and AgNO at 50 DEG C3Solution occur sufficient ion-exchange reactions, reaction 4h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain 13X type silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 1 hour at 50 DEG C, regulate pH to 9.5, continuing stirring 2 hours, the hydrazine hydrate solution adding 0.5mol/L continues stirring 3 hours, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of 13X type molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
17kg polylactic acid and 6kg polyoxyethylene are joined in 77kg methyl pyrrolidone, stirs at 80 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
16kg sulfonated polyether sulfone, 4kg carried metal silver molecular sieve, 8kg polyvinylpyrrolidone order are joined in 72kg trimethyl phosphate, stirs at 60 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 70 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 50 DEG C, extrudes with the rate of extrusion of 20 ml/min, 16 ml/min, 25 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 20 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, colibacillary antibiotic rate is 99% by prepared slowly released type antibiotic double-layer hollow fiber film.
Embodiment 6
A kind of preparation (6) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.25mol/LAgNO by the 10X type molecular sieve of 3kg and 60L concentration3Solution mixes, and is stirred, makes 13X type molecular sieve and AgNO at 80 DEG C3Solution occur sufficient ion-exchange reactions, reaction 5h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain 10X type silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 2 hours at 30 DEG C, regulate pH to 10, continuing stirring 2 hours, the glucose solution adding 0.8mol/L continues stirring 4 hours, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of 10X type molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
18kg polysulfones and 8kg polyvinylpyrrolidone are joined in 74kg trimethyl phosphate, stirs at 60 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
18kg polyacrylonitrile, 3kg carried metal silver molecular sieve, 7kg polyoxyethylene order are joined in 72kg trimethyl phosphate, stirs at 80 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 60 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 40 DEG C, extrudes with the rate of extrusion of 18 ml/min, 15 ml/min, 20 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 30 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, colibacillary antibiotic rate is 96% by prepared slowly released type antibiotic double-layer hollow fiber film.
Embodiment 7
A kind of preparation (7) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.5mol/LAgNO by the ZSM-5 molecular sieve of 2kg and 40L concentration3Solution mixes, and is stirred, makes ZSM-5 molecular sieve and AgNO at 80 DEG C3Solution occur sufficient ion-exchange reactions, reaction 4h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain ZSM-5 silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 2 hours at 60 DEG C, regulate pH to 10, continuing stirring 2 hours, the sodium borohydride solution adding 1mol/L continues stirring 4 hours, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of ZSM-5 molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
20kg cellulose acetate and 5kg polyoxyethylene are joined in 75kg hexamethyl phosphoramide, stirs at 80 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
18kg polyether sulfone, 2kg carried metal silver molecular sieve, 7kg Polyethylene Glycol order are joined in 73kg triethyl phosphate, stirs at 70 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 75 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 20 DEG C, extrudes with the rate of extrusion of 15 ml/min, 13 ml/min, 18 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 25 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, colibacillary antibiotic rate is 96% by prepared slowly released type antibiotic double-layer hollow fiber film.
Embodiment 8
A kind of preparation (8) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.3mol/LAgNO by the Y type molecular sieve of 3kg and 45L concentration3Solution mixes, and is stirred, makes Y type molecular sieve and AgNO at 40 DEG C3Solution occur sufficient ion-exchange reactions, reaction 6h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain Y type silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 2 hours at 30 DEG C, regulate pH to 9, continuing stirring 2 hours, the formalin adding 0.5mol/L continues stirring 4 hours, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of Y type molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
22kg SPSF and 8kg Polyethylene Glycol are joined in 70kg oxolane, stirs at 40 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
19kg Kynoar, 3kg carried metal silver molecular sieve, 8kg polyvinylpyrrolidone order are joined in 70kg dimethylformamide, stirs at 40 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 40 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 20 DEG C, extrudes with the rate of extrusion of 8 ml/min, 6 ml/min, 9 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 40 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, colibacillary antibiotic rate is 96% by prepared slowly released type antibiotic double-layer hollow fiber film.
Embodiment 9
A kind of preparation (9) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.5mol/LAgNO by the 4A molecular sieve of 5kg and 30L concentration3Solution mixes, and is stirred, makes 4A molecular sieve and AgNO at 50 DEG C3Solution occur sufficient ion-exchange reactions, reaction 5h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain 4A silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 2 hours at 50 DEG C, regulate pH to 8.5, continuing stirring 1 hour, the glucose solution adding 1mol/L continues stirring 4 hours, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of 4A molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
25kg sulfonated polyether sulfone and 8kg polyoxyethylene are joined in 67kg triethyl phosphate, stirs at 60 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
20kg polysulfones, 5kg carried metal silver molecular sieve, 10kg Polyethylene Glycol order are joined in 65kg dimethyl acetylamide, stirs at 70 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 60 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 30 DEG C, extrudes with the rate of extrusion of 12 ml/min, 10 ml/min, 15 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 30 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, colibacillary antibiotic rate is 99% by prepared slowly released type antibiotic double-layer hollow fiber film.
Embodiment 10
A kind of preparation (10) of antibacterial double-layer hollow fiber film
(1) preparation of carried metal silver molecular sieve
It is 0.5mol/LAgNO by the Y type molecular sieve of 2kg and 40L concentration3Solution mixes, and is stirred, makes Y type molecular sieve and AgNO at 60 DEG C3Solution occur sufficient ion-exchange reactions, reaction 4h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain Y type silver molecular sieve. Then by its ultrasonic disperse in deionized water, stir 2 hours at 50 DEG C, regulate pH to 9, continuing stirring 2 hours, the glucose solution adding 0.8mol/L continues stirring 3 hours, is finally centrifuged, clean with deionized water, after vacuum drying, obtain carried metal silver molecular sieve. Wherein, the mean diameter of Y type molecular sieve is not more than 1 micron.
(2) preparation of internal layer casting solution
25kg Kynoar and 5kg polyoxyethylene and polyvinylpyrrolidone are joined in 70kg triethyl phosphate and dimethyl acetylamide, stirs at 70 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
20kg polyacrylonitrile, 2kg carried metal silver molecular sieve, 9kg Polyethylene Glycol and polyvinylpyrrolidone order are joined in 69kg dimethyl sulfoxide and methyl pyrrolidone, stirs at 70 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 70 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 40 DEG C, extrudes with the rate of extrusion of 7 ml/min, 6 ml/min, 10 ml/min respectively. After casting solution sprays from spinneret exits, through the air gap of 30 centimetres, enter tank and solidify, form double-layer hollow fiber film, be finally collected by up-coiler, the slowly released type antibiotic double-layer hollow fiber film of preparation is soaked standby in deionized water.
After tested, colibacillary antibiotic rate is 96% by prepared slowly released type antibiotic double-layer hollow fiber film.
Comparative example 1
Slowly released type antibiotic fibrous membrane and the common available in non-time-release type silver-ion fiber film of the present invention have been carried out antibacterial ability contrast test by inventor, and evaluation methodology is the anti-microbial property evaluation methodology of fibrous membrane of the present invention. The preparation of common available in non-time-release fiber type film and the anti-bacterial result contrast are as shown in table 1.
The preparation of common available in non-time-release fiber type film
(1) preparation of silver molecular sieve
It is 0.1mol/LAgNO by the Y type molecular sieve of 0.5kg and 2.5L concentration3Solution mixes, and is stirred, makes Y type molecular sieve and AgNO at 40 DEG C3Solution occur sufficient ion-exchange reactions, reaction 8h after, by centrifugation, then with in deionized water wash to washing liquid without Ag+, then vacuum drying, obtain Y type silver molecular sieve.
(2) preparation of internal layer casting solution
12kg Kynoar and 2kg Polyethylene Glycol are joined in 86kg trimethyl phosphate, stirs at 60 DEG C, form uniform solution.
(3) preparation of outer layer casting solution
8kg polyimides, 0.5kg carried metal silver molecular sieve, 3kg polyvinylpyrrolidone order are joined in 88.5kg hexamethyl phosphoramide, stirs at 60 DEG C, form uniform solution.
(4) coextrusion one-step shaping method prepares antibacterial double-layer hollow fiber film
Inside and outside layer casting solution is stood under 40 DEG C and negative pressure state deaeration in 24 hours, then in triple channel spinning head, together with the core liquid of 20 DEG C, extrudes with the rate of extrusion of 1 ml/min, 0.8 ml/min, 1 ml/min respectively. After casting solution sprays from spinneret exits, it is directly entered tank to solidify, form the double-layer hollow fiber film containing silver molecular sieve, finally it is collected by up-coiler, the antibacterial double-layer hollow fiber film of preparation is soaked standby in deionized water, within first 3 days, changed a water every 24 hours, after 3 days, changed a water every 7 days.
Table 1 slowly released type antibiotic fibrous membrane and the contrast of common silver-ion fiber film antibiotic rate
Result and discussion:
Compared with common available in non-time-release type anion fiber film, the slowly released type antibiotic double-layer hollow fiber film of the present invention still has higher anti-microbial property after long-time placement.
The all documents mentioned in the present invention are incorporated as reference all in this application, are individually recited as reference such just as each section of document. In addition, it is to be understood that after the above-mentioned teachings having read the present invention, the present invention can be made various changes or modifications by those skilled in the art, these equivalent form of values fall within the application appended claims limited range equally.
Claims (10)
1. a slowly released type antibiotic double-layer hollow fiber film, it is characterised in that described fibrous membrane is cannulated structure, and described fibrous membrane includes:
(1) outer layer;
(2) internal layer being combined with each other with outer layer;
Wherein, described outer layer includes the first polymer and the carried metal silver molecular sieve being doped in described first polymer;
Described internal layer includes the second polymer.
2. double-layer hollow fiber film as claimed in claim 1, it is characterised in that described double-layer hollow fiber film, its external diameter is 1100��1500 microns, and/or internal diameter is 500��700 microns.
3. double-layer hollow fiber film as claimed in claim 1, it is characterized in that, described double-layer hollow fiber film, the material of its first polymer is selected from lower group: Kynoar, SPSF, sulfonated polyether sulfone, polyacrylonitrile, polyimides, polylactic acid, polyether sulfone, polysulfones, cellulose acetate, or its combination.
4. double-layer hollow fiber film as claimed in claim 1, it is characterized in that, described double-layer hollow fiber film, the material of its second polymer is selected from lower group: Kynoar, polyacrylonitrile, polyimides, polylactic acid, polyether sulfone, polysulfones, cellulose acetate, or its compositions.
5. double-layer hollow fiber film as claimed in claim 1, it is characterised in that described double-layer hollow fiber film, its internal layer thickness is 100��500 microns, and/or outer layer thickness is 40��120 microns.
6. double-layer hollow fiber film as claimed in claim 1, it is characterized in that, described double-layer hollow fiber film outer layer comprises the molecular sieve of the carried metal silver of the 2.5wt%��62.5wt% accounting for outer layer the first polymer, and in wherein said carried metal silver molecular sieve, silver carrying amount is 2��10wt% of carried metal silver molecular sieve gross weight.
7. double-layer hollow fiber film as claimed in claim 1, it is characterised in that described double-layer hollow fiber film has the one or more features selected from lower group:
I () is 30��70 nanometers at the pore diameter range of the outer surface of described double-layer hollow fiber film;
(ii) pure water flux is 400��800L/ (m under the pressure of 0.1MPa2��h-1)��
8. the method preparing slowly released type antibiotic double-layer hollow fiber film as claimed in claim 1, it is characterised in that said method comprising the steps of:
(1) internal layer casting solution and outer layer casting solution are provided;
Wherein, described outer layer casting solution contains the first polymer, carried metal silver molecular sieve, porogen, solvent; With
Described internal layer casting solution contains the loose structure of the second polymer, porogen, solvent;
(2) coextrusion one-step shaping method is adopted to prepare double-layer hollow fiber film.
9. method as claimed in claim 7, it is characterised in that the method also includes providing carried metal silver molecular sieve, and the preparation of described carried metal silver molecular sieve comprises the following steps:
(1) utilize molecular sieve and silver ion solution, prepare silver molecular sieve; With
(2) utilize reducing agent and silver molecular sieve, prepare carried metal silver molecular sieve.
10. goods, it is characterised in that described goods are containing, for example described slowly released type antibiotic double-layer hollow fiber film arbitrary in claim 1��6.
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| CN110449033A (en) * | 2019-08-27 | 2019-11-15 | 湖北中泉环保技术有限公司 | The cleaning method of ultrafiltration membrane surface organic sediment |
| CN114917769A (en) * | 2022-05-24 | 2022-08-19 | 江苏诺莱智慧水务装备有限公司 | Antibacterial hollow fiber membrane and preparation method thereof |
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| CN103285740A (en) * | 2012-02-23 | 2013-09-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method of antibacterial double-layer hollow fibrous membrane |
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| CN102489168A (en) * | 2011-12-12 | 2012-06-13 | 张一琛 | Preparation method of inorganic/organic hybridization antibacterial film |
| CN103285740A (en) * | 2012-02-23 | 2013-09-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method of antibacterial double-layer hollow fibrous membrane |
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| CN109745868A (en) * | 2019-01-25 | 2019-05-14 | 广东省医疗器械研究所 | It is a kind of for treating the preparation method of uremic antibacterial hollow-fibre membrane |
| CN110449033A (en) * | 2019-08-27 | 2019-11-15 | 湖北中泉环保技术有限公司 | The cleaning method of ultrafiltration membrane surface organic sediment |
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