CN102198374A - Asymmetric polyvinylidene fluoride microporous membrane with high intensity and preparation method thereof - Google Patents
Asymmetric polyvinylidene fluoride microporous membrane with high intensity and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an asymmetric polyvinylidene fluoride (PVDF) microporous membrane with high intensity and a preparation method thereof. Particularly the invention provides a method for preparing the polyvinylidene fluoride microporous membrane by adding a surface active agent, wherein the surface active agent is preferably a fluorocarbon surface active agent. In a non-solvent phase separation process, on the one hand, the surface active agent and polyvinylidene fluoride macromolecules are cross-linked and hybridized, therefore, the crystalline property of the polyvinylidene fluoride is reduced, the liquid-liquid phase separation is promoted, the crystals are effectively prevented from being agglomerated in the film-forming process of the polyvinylidene fluoride, and the intensity is improved; on the other hand, proved by accidental discovery, a thermodynamic mass transport process is changed by adding the surface active agent so that the asymmetric polyvinylidene fluoride microporous membrane can be prepared. The membrane disclosed by the invention is wide in application, such as clearing and filtering of food/beverage, sterilizing and filtering of medical preparation and the like.
Description
Technical field
The present invention relates to high molecular polymer microporous separation membrane technical field.Film of the present invention has high strength, film aperture on thickness direction and has dissymmetrical structure.
Background technology
The high molecular polymer microporous barrier is a new high-tech industry that abroad grows up in the 1970's, belongs to film and separates category.Various diffusion barriers are pressed the magnitude classification in film space, are divided into usually from small to large: reverse osmosis membrane (reverse osmosis membrane), NF membrane (nano-filtration membrane), milipore filter (ultrafiltration membrane), microporous barrier (micro-filtration membrane).Reverse osmosis membrane is generally used for desalinization, ultra-pure water and produces etc. on using, NF membrane is generally used in the water removal of big metal ions such as low molecule and calcium, magnesium, milipore filter then is generally used for the separation of Polymer Solution, the application of microporous barrier is then more complicated extensively, clarification filtration as food and drink, the aseptic filtration of pharmaceutical preparation is as wastewater membrane bioreactor construction assembly etc.
The reparation technology of microporous barrier is divided into non-solvent usually and causes phase separation method, thermally induced phase separation and pulling method.Wherein non-solvent causes the basic principle of phase separation method and is exactly: earlier polymer and certain amount of solvent and poor solvent or gel are mixed, be mixed with stable or metastable polymer under certain condition, solvent, poor solvent or gel mixed liquor, then mixed liquor is supported in glass plate or the annular polishing steel band that rotates continuously or polishing rotary drum or nonwoven with certain thickness curtain coating, change the existence condition of casting solution then, evaporate as solvent, non-solvent immersion etc., original stable or metastable casting solution can be separated because of the variation of internal component content, be usually expressed as casting solution and become muddy, bleach then, produce microcellular structure.The basic principle of thermally induced phase separation is: earlier polymer is mixed with poor solvent, heat temperature raising, make polymer dissolution become the mixed liquor of homogeneous phase, under heat-retaining condition, mixed liquor is supported in glass plate or the annular polishing steel band that rotates continuously or polishing rotary drum or nonwoven with certain thickness curtain coating, cooling makes it to be separated then, produces microporous barrier.The basic principle of pulling method is: the melt high molecular polymer is rolled in advance, and the vertical or cross directional stretch with different rates carries out thermal finalization afterwards again and handles then, forms microporous barrier.
Microporous barrier can be divided into symmetric membrane and asymmetric membrane (or anisotropic membrane) by structure.Known in the field, symmetric membrane is film has the basically identical size on thickness direction aperture; Asymmetric membrane is film has the unanimity do not finished on thickness direction aperture, be often referred to the thickness direction aperture and have the film that gradient magnitude changes, comprise that also first increase the in aperture afterwards reduces or reduce earlier afterwards to increase, even thickness direction part aperture there is the indeclinable film of a graded part.
Chinese patent ZL200410067007.1 discloses and a kind ofly has been equipped with the method for polyvinylidene fluoride hollow-fibre membrane with the melt spinning-pull stretching legal system, and melt spinning, stretching and thermal finalization technology film forming do not need solvent and additive in the preparation process of film.Chinese patent ZL200410067002.9 discloses a kind of method for preparing the polyvinylidene fluoride hollow fiber microporous membrane with microscopic phase separating method, described method is the improvement of traditional melt spinning-stretching technique, with polyvinylidene fluoride resin and hydrophilic organic material or inorganic pellet melt blending, prepared film all increases at aspects such as pore size and hydrophilies before melt spinning.
U.S. Pat 5022990 discloses a kind of being separated with heat and has prepared the method for polyvinylidene fluoride perforated membrane, this method is with polyvinylidene fluoride resin and organic liquid and inorganic granular mixing, being separated through heat then melt extrudes into the blend of gained the film of hollow fiber, tubulose or flat, at last organic liquid and inorganic pellet is extracted.Chinese patent ZL200510126253.4 discloses a kind of polyvinylidene fluoride perforated membrane and preparation method thereof, a suitable solvent---benzophenone has particularly been proposed, by reducing polyvinylidene fluoride-benzophenone system temperature, initiation is separated, and prepares the polyvinylidene fluoride perforated membrane.This polyvinylidene fluoride porous film surface does not have obvious cortex construction, and the film section is the homogeneous spongelike structure, increases with polyvinylidene fluoride concentration, and it is tightly packed to present bulk, and membrane aperture is distributed as 1～0.01 μ m.
Non-solvent causes phase separation method and is specially adapted to the asymmetric microporous barrier of preparation.Disclose with non-solvent in the U.S. Pat 4629563 of application in 1981 and caused the method that phase separation method prepares asymmetric microporous barrier.The U.S. US5171445 of application in 1991 improves the method, has reduced cast temperature and gelling temp, has reduced the sensitiveness of film to technological parameter, makes that processing technology is simpler, repeatability is better.The asymmetric microporous barrier of above-mentioned document indication has during filtration and well holds back efficient and filtration flow-rate in film thickness direction pore size graded.Polysulfones is particularly suitable for preparing asymmetrical film, in US4629563, point out, its prescription is non-homogeneous solution, comprise two phases of separating, wherein one is polymer-rich phase mutually, and another is polymer-poor phase mutually, and two-phase has identical constituent and comprises high molecular polymer, solvent, pore-foaming agent and additive, polymer-rich phase has higher polymer concentration, and polymer-poor phase then is rich in solvent.When induce the branch phase time in coagulation bath, this Unstable Systems forms fine and close cortex rapidly at the interface, and then influences inner phase-splitting, forms the asymmetric membrane with gradient pore size.Polyvinylidene fluoride is a crystalline polymer, and its mechanism difference that is separated is not seen patent and document that big gradient unsymmetric structure is arranged.Japanese firm " FUJI " has announced patent US4933081 pvdf membrane with two degree dissymmetrical structures in 1988 in the U.S., reduces gradually to increase gradually then earlier at the film thickness direction bore dia, and hole agent variable gradient is less." FUJI " membrane process characteristics are earlier through damp atmosphere exposure relatively before coagulation bath solidifies, has higher polyvinylidene fluoride pyrrolidones (PVP) in the prescription, this is a kind of pore-foaming agent and cosolvent, and the dissolving loss causes new filtrate contamination easily in the film use.The situation of degree of crystallinity size and film-strength when in addition, " FUJI " prescription does not relate to film forming.Patent JP2006314651 of toray Co., Ltd. and JP2006312464 all disclose a kind of fluoropolymer double-layered compound film, this fluoropolymer diffusion barrier has tridimensional network layer and chondritic layer, described tridimensional network layer is substantially free of aperture 5 μ m or bigger micropore, chondritic has the aperture of 0.1-5 μ m, makes the film of gained have good separating property and physical strength.Its shortcoming is the technology more complicated, and described technically composite membrane also can be thought asymmetric, but the service life of film is not as aperture continually varying asymmetric membrane.
Prior art as seen, the PVDF membrane preparation methods mainly contains three kinds: non-solvent causes phase inversion (DIPS), thermic phase inversion (TIPS) and pulling method.Because the polyvinylidene fluoride macromolecule is a those semi-crystalline materials, the Polymer Solution system is easy to crystallization and induces the generation gel, when adopting the non-solvent phase inversion to prepare membrane material, thereby Polymer Solution is induced by non-solvent and is made polymer crystallization undergo phase transition to get off structure is fixed.Yet we find because the accumulation institute film forming structural strength of polymer crystal is low.High molecular content is usually than higher in the polyvinylidene fluoride process because thermally induced phase separation prepares, and it directly influences transparent performance; To be separated mainly be to utilize thermal induction to be separated to heat in addition, and thermal induction is carried out in whole film rapidly, and the film of gained is the film of isotropism symmetrical structure.The PVDF membrane of pulling method preparation mostly is hollow-fibre membrane, and flat sheet membrane is not seen the patent documentation report, does not also relate to the microporous barrier of dissymmetrical structure.In existing technology, also there is not a kind of pvdf membrane that high-intensity bore diameter gradient changes that has.Thereby, can't make bore diameter gradient change and excellent in strength obtains unifying at the pvdf membrane of all prior arts, limited the application of pvdf membrane.
Summary of the invention
Technical solution of the present invention is to provide asymmetric polyvinylidene fluoride of a kind of high strength (PVDF) and preparation method thereof.Realize the present invention by add surfactant in casting solution, preferred surfactants is a fluorocarbon surfactant.Cause in the phase separation at non-solvent, on the one hand surfactant and polyvinylidene fluoride macromolecule crosslinking hybrid have reduced the crystal property of polyvinylidene fluoride, promotion liquid-liquid phase-splitting, effectively avoid crystalline solid accumulation in the polyvinylidene fluoride film forming procedure, improved intensity; On the other hand, unexpected discovery, the interpolation of surfactant has changed the thermodynamics mass transport process, can prepare asymmetric polyvinylidene fluoride microporous barrier.
According to first aspect present invention, a kind of pvdf membrane of dissymmetrical structure is provided, this film contains the micropore surface of a minimum aperture, and a reverse side that contains largest hole is the loose structure that the aperture increases along the aperture face to macropore face gradient between the two sides.The about 0.05-0.5 μ of the average pore size m of film aperture face of the present invention, the about 3-20 μ of the average pore size of macropore face m, the flow of water is 10-100L/m
2.min.bar.
According to second aspect present invention, a kind of pvdf membrane of dissymmetrical structure is provided, dissymmetrical structure described here refers to film thickness direction aperture elder generation gradient increases the consistent structure of back trend.Film of the present invention, along thickness direction the pore size of 30% film being arranged approximately is that gradient increases, remaining part membrane aperture size basically identical, the about 0.1-1 μ of the average pore size m of film aperture face of the present invention, the about 2-10 μ of the average pore size of macropore face m, the flow of water is 5-70L/m
2.min.bar.
According to third aspect present invention, provide a kind of based on liquid-liquid phase-splitting, high-intensity pvdf membrane.Studies show that polyvinylidene fluoride high score solution after immersing coagulation bath, becomes thermodynamic unstable system, liquid-liquid phase separation or liquid-solid phase can take place separate.Liquid-liquid phase-splitting is instantaneous phase-splitting, and liquid-solid phase-splitting is time-delay phase-splitting, the i.e. process of crystallization.During polyvinylidene fluoride macromolecule non-solvent phase inversion, crystallization will reduce the mechanical strength performance of material.In order to reduce the degree of crystallinity of polyvinylidene fluoride film forming, promote liquid-liquid phase-splitting, make polyvinylidene fluoride macromolecule of the present invention and the preferred fluorine surfactant of surfactant blend, the high molecular hydridization of polyvinylidene fluoride reduces its crystallizing power on the one hand, surfactant promotes the thermodynamic unstable system mass transfer on the other hand, forms being separated based on liquid-liquid phase-splitting.Film of the present invention can prepare with PVDF HYLAR-461, can be with the fluorine surfactant that contains about 0.1% to 15% weight, as Fluorad FC-170C, FC-430, FC-431; Surflon S-141, S-145; Outstanding Nirn DS-401, DS-402 etc.Prepared film, PVDF degree of crystallinity are less than 50%, and fracture strength is 2-12 newton in the stretching experiment, and the fracture extensibility is 10-70%.
According to fourth aspect present invention, provide the preparation method of the asymmetric pvdf membrane of a kind of high strength.Comprise the following steps:
With content is the PVDF macromolecule of 8%-20% weight, and as PVDF HYLAR-461, content is the surfactant of 0.5%-15% weight, and as Fluorad FC-170C, and the additive of 0.1-5% is dissolved in organic solvent formation casting solution as batching.Above-mentioned casting solution forms nascent film by the even blade coating of scraper on glass or bright steel band face under temperature.Then, the film of will coming into being immerses gel water-bath phase-splitting, obtains the PVDF microporous barrier.Newly-generated microporous barrier can immerse weight content and be in the aqueous solution of 2%KOH and 2% hydrogen peroxide 48 hours after pure water washing, made film hydrophilic.
In the casting step of this method, described organic solvent, has the characteristic of dissolving each other with water, as N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, trimethyl phosphate, triethyl phosphate, acetone, r-butyrolactone etc. one or more, the temperature of ingredients mixture can be at 30 ℃-80 ℃, preferred temperature is 30 ℃-50 ℃, about 30 ℃-80 ℃ of the temperature of gel water-bath.Additive can be inorganic salts such as LiCl, NH
4Cl or organic molecule are as acetone, butanone, oxolane etc.
The additive that adopts among the present invention is mainly inorganic salts and organic molecule class, be mainly used in the raising porosity, improve permeability, as LiCl, the amount of adding is usually below 5%, if the amount of adding is too high, be difficult to obtain the casting solution of homogeneous on the one hand, the mechanical property of the film of feasible preparation reduces on the one hand.
High-intensity acquisition mode mainly is by promoting liquid-liquid phase-splitting among the present invention, degree of crystallinity when reducing the PVDF film forming, can be realized by two kinds of technical schemes: (1) adds surfactant, divide phase time to promote the mass transfer of thermodynamic unstable system, make that the instantaneous phase-splitting of liquid-liquid phase-splitting is main phase-splitting.(2) add noncrystalline additive in the casting solution, described noncrystalline additive preferably has the compatibility preferably with PVDF, makes the PVDF film forming make strand hydridization, forms difficult crystallizing system, make that the non-crystalline structure of liquid-liquid phase-splitting is main, and reduce the accumulation crystal grain that liquid-solid phase-splitting forms.Surfactant of the present invention preferably uses carbon fluorine class surfactant, as Fluorad FC-170C.We find that unexpectedly the interpolation of surfactant has changed the thermodynamics mass transport process, and the prepared film of the present invention has asymmetric structure.We also find, add the surfactant of high level, usually at 5%-15%, preferred 8%-12%, the easier bore diameter gradient increase that makes film develops into the bottom, and lower surfactant usually below 3%, then forms the microporous barrier that thickness direction aperture elder generation gradient increases the consistent structure of back trend.
Description of drawings:
Fig. 1 is with the section micro-structure diagram of ESEM to the polyvinylidene fluoride microporous barrier produced among the embodiment 1;
Fig. 2 is with the section micro-structure diagram of ESEM to the polyvinylidene fluoride microporous barrier produced among the embodiment 2;
The specific embodiment:
Below in conjunction with embodiment and accompanying drawing the present invention is further described, embodiment will help to understand the present invention better, but the present invention is not limited only to following embodiment.
The PVDF microporous barrier that embodiment 1 thickness direction bore diameter gradient changes
We have disposed weight content is that 13.7% PVDF macromolecule HYLAR-461,9.7% fluorine surfactant FC-170,4% water, 1% LiCl and 71.6% dimethylacetylamide (DMAC) are the casting stoste of solvent.Used thickness is that the scraper of 300 μ m evenly is coated in Polymer Solution on the glass plate under 70 ℃ of states, stops in the water-bath of immersing 60 ℃ after 5 seconds to divide solidifying in the air of room temperature humidity 70%.After the curing, film washs with pure water, immerse to immerse weight content then and be in the aqueous solution of 2%KOH and 2% hydrogen peroxide 48 hours, makes film hydrophilic.The about 0.1 μ m of the average pore size of film aperture face, the about 15 μ m of the average pore size of macropore face, the about 160 μ m of the thickness of film, the flow of water is 70L/m2.min.bar, and fracture strength is 6 newton in the stretching experiment, and the fracture extensibility is 30%.
Fig. 1 has provided the representational SEM section of sample film photo.Can see that by figure film internal orifice dimension size has tangible gradient-structure, promptly the pore size gradient increases on the thickness direction from the aperture face to the macropore face.
Embodiment 2 thickness direction apertures elder generation gradient increases the consistent PVDF microporous barrier of back trend
We have disposed weight content is that 18.5% PVDF macromolecule HYLAR-461,3% fluorine surfactant FC-170,2% water, 0.5% LiCl and 78% dimethylacetylamide (DMAC) are the casting stoste of solvent.Used thickness is that the scraper of 300 μ m evenly is coated in Polymer Solution on the glass plate under 70 ℃ of states, stops in the water-bath of immersing 60 ℃ after 5 seconds to divide solidifying in the air of room temperature humidity 70%.After the curing, film washs with pure water, immerse to immerse weight content then and be in the aqueous solution of 2%KOH and 2% hydrogen peroxide 48 hours, makes film hydrophilic.The about 0.3 μ m of the average pore size of film aperture face, the about 3 μ m of the average pore size of macropore face, the about 125 μ m of the thickness of film, the flow of water is 30L/m2.min.bar, and fracture strength is 8 newton in the stretching experiment, and the fracture extensibility is 60%.
Fig. 2 has provided the representational SEM section of sample film photo.Can see that by figure film internal orifice dimension size then tends to the consistent macropore face that develops into again from the increase of aperture face gradient.
The influence of embodiment 3 polymer concentrations
We have disposed weight content is that 12.5% PVDF macromolecule HYLAR-461,2.5% fluorine surfactant FC-170,4% water, 0.5% LiCl and 82% dimethylacetylamide (DMAC) are the casting stoste of solvent.Press the step system film of embodiment 2 then, we find that the finger-like macropore has appearred in prepared film.
Embodiment 4 Temperature Influence
We have disposed weight content is that 13.2% PVDF macromolecule HYLAR-461,7% fluorine surfactant FC-170,0.8% water and 83% dimethylacetylamide (DMAC) are the casting stoste of solvent.Used thickness is that the scraper of 300 μ m evenly is coated in Polymer Solution on the glass plate under 60 ℃ of states, stops in the water-bath of immersing 50 ℃ after 3 seconds to divide solidifying in the air of room temperature humidity 50%.After the curing, film washs with pure water, immerse to immerse weight content then and be in the aqueous solution of 2%KOH and 2% hydrogen peroxide 48 hours, makes film hydrophilic.Fracture strength is 5 newton in the stretching experiment, and the fracture extensibility is 38%.
Comparative Examples 1
Used thickness is that the scraper of 300 μ m evenly is coated in Polymer Solution on the glass plate under the casting stoste that configuration and embodiment 4 are identical, 45 ℃ of states, stops in the water-bath of 38 ℃ of immersions after 3 seconds to divide solidifying in the air of room temperature humidity 50%.Pressing embodiment 4 identical technologies after solidifying cleans and hydrophilic treated.Fracture strength is 3 newton in the stretching experiment, and the fracture extensibility is 15%.
Embodiment 5
We have disposed weight content is that 17.8% PVDF macromolecule HYLAR-461,8% fluorine surfactant FC-170,3% water, 0.8% LiCl and 70.4%N-methyl pyrrolidone (NMP) are the casting stoste of solvent.Used thickness is that the scraper of 300 μ m evenly is coated in Polymer Solution on the glass plate under 80 ℃ of states, stops in the water-bath of immersing 80 ℃ after 2 seconds to divide solidifying in the air of room temperature humidity 60%.After the curing, film washs with pure water, immerse to immerse weight content then and be in the aqueous solution of 2%KOH and 2% hydrogen peroxide 48 hours, makes film hydrophilic.Obtain the aperture is increased to the macropore face by aperture face gradient asymmetric microporous barrier, the about 0.1 μ m of the average pore size of aperture face, the about 20 μ m of the average pore size of macropore face, the about 140 μ m of the thickness of film, the flow of water is 43L/m2.min.bar, fracture strength is 9 newton in the stretching experiment, and the fracture extensibility is 30%.
Those of ordinary skill in the art will be appreciated that, more than several examples do not show the limited range of application of this patent.The method that any professional person that film preparation is familiar with can both set forth according to patent easily is applied to other any possible systems and obtains high performance film.
Claims (12)
1. a polyvinylidene fluoride (PVDF) microporous barrier is characterized in that, described film is a main component with the PVDF macromolecule, and PVDF degree of crystallinity is less than 50%; Film aperture on thickness direction has dissymmetrical structure.
2. film as claimed in claim 1 is characterized in that described dissymmetrical structure contains the micropore surface of a minimum aperture, and a reverse side that contains largest hole is the loose structure that the aperture increases along the aperture face to macropore face gradient between the two sides.
3. film as claimed in claim 2 is characterized in that, the about 0.05-0.5 μ of the average pore size of described minimum aperture micropore surface m, the about 3-20 μ of the average pore size of the reverse side of largest hole m.
4. as claim 2 or 3 described films, it is characterized in that the discharge of described film is 10-100L/m
2.min.bar fracture strength is 2-12 newton, and the fracture extensibility is 10-70%.
5. film as claimed in claim 1 is characterized in that, described dissymmetrical structure is that film thickness direction aperture elder generation gradient increases the consistent structure of back trend.
6. film as claimed in claim 5 is characterized in that, the about 0.1-1 μ of the average pore size of described minimum aperture micropore surface m, the about 2-10 μ of the average pore size of the reverse side of largest hole m.
7. as claim 5 or 6 described films, it is characterized in that the discharge of described film is 5-70L/m
2.min.bar, fracture strength is 2-12 newton, and the fracture extensibility is 10-70%.
8. the preparation method of a polyvinylidene fluoride microporous barrier, it is characterized in that, with content is the PVDF macromolecule of 8%-20% weight, content is that the surfactant of 0.5%-15% weight and the additive of 0.1-5% are dissolved in organic solvent formation casting solution as batching, above-mentioned casting solution is forming nascent film by the even blade coating of scraper under the 30-80 ℃ of temperature on glass or bright steel band face, then, the film of will coming into being immerses 30--80 ℃ of gel water-bath phase-splitting, obtain the PVDF microporous barrier, newly-generated microporous barrier makes film hydrophilic through pure hydrophilic PROCESS FOR TREATMENT.
9. preparation method as claimed in claim 8 is characterized in that, described surfactant is a fluorine surfactant.
10. preparation method as claimed in claim 8 is characterized in that, described hydrophilic treatment process is that film was immersed in the aqueous solution that weight content is 2%KOH and 2% hydrogen peroxide 48 hours.
11. preparation method as claimed in claim 8, it is characterized in that, described organic solvent has the characteristic of dissolving each other with water, is at least in N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, trimethyl phosphate, triethyl phosphate, acetone, the r-butyrolactone one or more.
12. preparation method as claimed in claim 8 is characterized in that, described additive is inorganic salts or organic molecule.
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| CN104362276A (en) * | 2014-10-27 | 2015-02-18 | 中国乐凯集团有限公司 | Polyethylene microporous membrane, preparation method and lithium ion battery |
| CN104492284A (en) * | 2014-12-29 | 2015-04-08 | 大连理工大学 | Double-sided asymmetrical-structure flat support membrane and preparation method and application thereof |
| CN108854593A (en) * | 2018-06-13 | 2018-11-23 | 山西大学 | A kind of high-throughput double excellent type PVDF plate membrane preparation methods with high rejection |
| CN109065811A (en) * | 2018-08-20 | 2018-12-21 | 湖南烁普新材料有限公司 | Aqueous PVDF coating diaphragm and its preparation method and application |
| CN109065811B (en) * | 2018-08-20 | 2021-08-27 | 湖南烁普新材料有限公司 | Water-based PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof |
| CN112267300A (en) * | 2020-09-11 | 2021-01-26 | 东华大学 | Electrostatic spinning fiber-based ultrathin continuous nano spider web fiber material and preparation method thereof |
| CN112267300B (en) * | 2020-09-11 | 2021-10-26 | 东华大学 | Electrostatic spinning fiber-based ultrathin continuous nano spider web fiber material and preparation method thereof |
| CN113843937A (en) * | 2021-10-08 | 2021-12-28 | 西安理工大学 | Migration-resistant hydrogel-based freshness colorimetric indication label and preparation method thereof |
| CN113843937B (en) * | 2021-10-08 | 2024-02-06 | 西安理工大学 | Migration-resistant hydrogel-based freshness colorimetric indication label and preparation method thereof |
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Effective date of registration: 20161129 Address after: Hangzhou City, Zhejiang province 310053 Xiaoshan River Town Village Zixia Patentee after: Hangzhou Cobetter Filtration Equipment Co., Ltd. Address before: Hangzhou City, Zhejiang province 310053 Xiaoshan River Town Village Zixia Patentee before: Hangzhou Feir Filter Technology Co., Ltd. |