CN114307650A - Sulfone polymer microporous liquid-stopping membrane and preparation method and application thereof - Google Patents

Sulfone polymer microporous liquid-stopping membrane and preparation method and application thereof Download PDF

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CN114307650A
CN114307650A CN202210055339.6A CN202210055339A CN114307650A CN 114307650 A CN114307650 A CN 114307650A CN 202210055339 A CN202210055339 A CN 202210055339A CN 114307650 A CN114307650 A CN 114307650A
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liquid
sulfone polymer
film
membrane
polymer microporous
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CN114307650B (en
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贾建东
蔡梁
吴枫
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Hangzhou Cobetter Filtration Equipment Co Ltd
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Hangzhou Cobetter Filtration Equipment Co Ltd
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Abstract

The invention relates to a sulfone polymer microporous liquid stopping membrane and a preparation method and application thereof, wherein the microporous liquid stopping membrane comprises a first porous surface, a second porous surface and a porous main body positioned between the first porous surface and the second porous surface; the porous body is internally provided with a non-directional tortuous passage and is characterized in that the sulfone polymer microporous liquid stopping film is used for stopping the injection liquid containing the plant extract; in the sulfone polymer microporous liquid stopping film, the ratio of the number of holes with the aperture not more than 2.5 mu m measured by a PMI aperture tester to the whole number of the holes is less than 10 percent; the porosity of the sulfone polymer microporous liquid stopper film is at least 60%; the water BP value of the sulfone polymer microporous liquid stopping film is 20-50KPa, and the liquid stopping height is at least 1 m. The sulfone polymer microporous liquid stopping membrane provided by the technical scheme of the invention has a more optimized membrane body structure and comprehensive performance, and has the advantages of large flux, stable flux, high filtration precision, excellent and stable liquid stopping performance and higher applicability when being applied to Chinese patent medicine liquid stopping.

Description

Sulfone polymer microporous liquid-stopping membrane and preparation method and application thereof
Technical Field
The invention relates to the technical field of liquid stopping membrane materials, in particular to a sulfone polymer microporous liquid stopping membrane and a preparation method and application thereof.
Background
Automatic liquid-stopping transfusion system (Airstop, also known as from drip stop, from sealing, prevent evacuation transfusion system), is a novel disposable medical consumables that replaces ordinary transfusion system, and its function is when the infusion process is accomplished, keeps the liquid level not descend for a long time at the assigned position, avoids the air to get into the vein automatically to alleviate nursing staff's operating pressure and patient psychological pressure.
In recent years, automatic liquid-stopping infusion sets have been widely popularized in European and American areas and are gradually popularized in China. The automatic liquid stopping infusion apparatus under the condition can be divided into a buoy structure and a membrane structure according to a design concept, the basic principle is consistent, when the infusion process is about to be finished, and the liquid level descends to a liquid stopping membrane, subsequent air can be blocked by the liquid stopping membrane and cannot continuously enter a lower catheter, and a liquid column in the lower catheter reaches a balance state under the action of self gravity, atmospheric pressure, human body venous pressure and upward gravitation generated by the liquid stopping membrane, so that the automatic liquid stopping is realized.
The existing domestic drip is usually western medicine drip and Chinese patent medicine drip, the Chinese patent medicine takes Chinese medicinal materials as raw materials, under the guidance of the theory of traditional Chinese medicine, in order to prevent and treat the need of the disease, process it into Chinese medicinal products of certain formulation according to prescribed prescription and preparation process, it is a kind of Chinese medicinal preparation of commercialization approved by the administrative department of state drug supervision; compared with western medicine drip infusion, large granular substances in the environment of the Chinese patent medicine drip infusion system are more.
Therefore, when the Chinese patent medicine drip liquid stopping agent is used for Chinese patent medicine drip liquid stopping, higher requirements are provided for the comprehensive properties of the liquid stopping film, such as flux and stability, liquid stopping height, filtering precision and the like; when PES is used as a Chinese patent medicine liquid stopping membrane, the PES membrane is required to have higher flux and more stable flux, because the viscosity and the density of the Chinese patent medicine are uniformly higher than those of western medicines, and the Chinese patent medicine contains more large-particle substances, wherein the large-particle substances are usually broken glass fragments at the bottle mouth of an ampoule bottle, partial effective components in Chinese patent medicine liquid and the like, and when the PES is infused for a long time, the large-particle substances intercepted in the liquid stopping membrane are continuously increased, so that the PES is not beneficial to the liquid medicine to pass through, the flux of the membrane is reduced, the infusion speed is reduced, and the infusion time is overlong, so that the discomfort of a patient can be caused; further, there are also the following problems:
1. because the flux of the membrane is small, the Chinese patent medicine liquid is usually obtained by plant extraction, so the viscosity and the density of the Chinese patent medicine are higher than those of western medicine prepared by solvent, after the Chinese patent medicine liquid passes through the membrane, the Chinese patent medicine and partial effective components thereof can be remained in the membrane, the curative effect of a patient is reduced, and the influence on the human health is further caused.
2. Because the flux of the membrane is unstable, after the infusion is carried out for a certain time, the flux of the membrane can be quickly attenuated, so that the flux of the membrane is reduced, the infusion speed is reduced, the infusion time is too long, and the discomfort of a patient can be caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the sulfone polymer microporous liquid stopping membrane which is applied to Chinese patent medicine infusion and has large and stable flux and excellent comprehensive performance and the method for preparing the sulfone polymer microporous liquid stopping membrane, so as to solve the problems of small flux, unstable flux and poor comprehensive performance of the existing liquid stopping membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sulfone polymer microporous liquid stop membrane comprising a first porous surface, a second porous surface, and a porous body located between the first porous surface and the second porous surface, the porous body having non-directional tortuous pathways therein, the sulfone polymer microporous liquid stop membrane being for stopping an injection liquid containing a botanical extract;
in the sulfone polymer microporous liquid stopping film, the ratio of the number of holes with the aperture not more than 2.5 mu m measured by a PMI aperture tester to the whole number of the holes is less than 10 percent;
the porosity of the sulfone polymer microporous liquid stopper film is at least 60%;
the water BP value of the sulfone polymer microporous liquid stopping film is 20-50KPa, and the liquid stopping height is at least 1 m.
The sulfone polymer microporous liquid stopping membrane provided by the invention is used for injecting plant-containing extract liquidThe liquid injection is especially suitable for application in density higher than 1.02g/cm3And the viscosity is more than 1.25 cps; wherein the plant extractive solution can be Chinese medicinal liquid, such as SHENMAI injection, Carthami flos injection, QINGKAILING injection, etc.; the density and viscosity of the Chinese patent medicine liquid are generally higher than those of the western medicine liquid, and large granular substances (Chinese patent medicine active ingredients, broken glass slag at the opening of an ampoule bottle and the like) in an environmental system of the Chinese patent medicine liquid are more, so that it can be understood that when the Chinese patent medicine liquid passes through the membrane, part of the large granular substances can block holes of the membrane, and the flux attenuation of the membrane is too fast; the density and the viscosity of the Chinese patent medicine liquid are both greater than those of the western medicine liquid, namely the friction force between the Chinese patent medicine liquid and the membrane is greater than that between the western medicine liquid and the membrane, so that the flux of the Chinese patent medicine liquid between the membranes is less than that of the western medicine liquid, and in order to ensure the comfort of a patient during transfusion, the sulfone polymer microporous liquid stopping membrane has greater flux, so that the flux of the membrane is not reduced due to the large density and the large viscosity of the liquid when the Chinese patent medicine liquid passes through the sulfone polymer liquid stopping membrane; the flux of the sulfone polymer microporous liquid stopping membrane is relatively stable, namely, the flux attenuation of the membrane is slow as the Chinese patent medicine liquid passing through the membrane is increased along with the increase of the infusion time; in the sulfone polymer microporous liquid stopping membrane, the ratio of the number of holes with the aperture not more than 2.5 μm to the total number of the holes is less than 10%, preferably 3-8%, wherein the holes with the aperture not more than 2.5 μm measured by PMI are defined as small holes, the ratio of the number of the small holes to the total number of the holes cannot be too large, otherwise, the smaller the aperture and the larger the number of the small holes are, the more the Chinese patent medicine liquid passes through the membrane, the smaller the flux of the Chinese patent medicine liquid in unit time is caused, and the Chinese patent medicine liquid contains more large-particle substances which are usually configured as Chinese patent medicines, the glass residue at the bottle mouth of the ampoule bottle falls into the liquid medicine, the particle size of the particles is larger, and when the number of the small holes is larger, the particles block more small holes, thereby causing the flux of the Chinese patent medicine liquid in unit time to be reduced or even the Chinese patent medicine liquid cannot pass through the membrane, so that the transfusion time of the patient is prolonged, and the physical discomfort and psychological anxiety of the patient can be caused; meanwhile, the number of the small holes accounts for the holesThe ratio of the whole quantity cannot be too small, the small holes ensure that the surface tension between the Chinese patent medicine liquid and the membrane is larger, the capillary phenomenon generated when the Chinese patent medicine liquid enters the membrane is strong, the membrane is ensured to realize liquid stopping, and the liquid stopping height is at least 1 m; and when the number of the small holes is too small, the filtering precision of the membrane is reduced.
The porosity is the proportion of the membrane pore volume of the liquid stopping membrane to the total volume, the sulfone polymer microporous liquid stopping membrane of the invention is formed by sequentially arranging a first porous surface, a porous main body and a second porous surface along the thickness direction, wherein the porous body is provided with non-directional tortuous paths which refer to randomly oriented groove structures and/or discretely distributed hole structures, and the non-directional tortuous passages are communicated with each other, the liquid medicine flows in from the second porous surface, flows through the passages and flows out from the first porous surface, the volume of the groove structure and the hole structure accounts for at least 60 percent of the total volume of the membrane, preferably more than 70 percent, when the membrane is completely wetted by the Chinese patent medicine liquid, the Chinese patent medicine liquid in the membrane accounts for at least 70%, the Chinese patent medicine liquid in unit time has larger volume and higher porosity when passing through the membrane, and further ensures that the sulfone polymer microporous liquid stopping membrane has higher flux.
The model of the PMI pore size tester is CFP-1J00AEX, the pore size distribution of the sulfone polymer microporous liquid stopping membrane is measured by using a gas-liquid and liquid-liquid discharge method, and parameters such as the PMI pore size, the porosity and the like can be tested by tearing the sulfone polymer microporous liquid stopping membrane open first and testing corresponding parameters of the sulfone polymer microporous liquid stopping membrane; or the film cross-sectional structure is subjected to morphology characterization by using a scanning electron microscope, and then is measured and measured by using computer software (such as Matlab, NIS-Elements and the like) or manually; of course, the skilled person can also obtain the above parameters by other measuring means, which are only used as reference.
The sulfone polymer microporous liquid stopping membrane provided by the invention has good liquid stopping performance, high and stable liquid stopping height, and no backflow; preferably, the liquid stopping height of the membrane is more than 1.5 m; the sulfone polymer microporous liquid stopping film generates surface tension with Chinese patent medicine liquid to balance hydrostatic pressure of the liquid medicine between the film and a needle head, so that liquid stopping is realized.
Preferably, the sulfone polymer microporous liquid-stopping membrane has a negative charge density per unit area of not more than 70 x 10^-9mol/cm2Preferably (20-55) × 10^ s-9mol/cm2(ii) a The unit mass negative charge density of the sulfone polymer microporous liquid stopping film is not more than 150 x 10^-10mol/mg。
The unit area negative charge density of the sulfone polymer microporous liquid stopping film is preferably (30-40) × 10^-9mol/cm2The negative charge density per unit mass is preferably (70-100) × 10^-10mol/mg; it can be understood that the specific surface area of the sulfone polymer micropore liquid stopping film can not be too large, namely, the contact area between the Chinese patent medicine liquid and the membrane when the Chinese patent medicine liquid passes through the membrane should not be too large, the negative charge density is larger, the adsorption capacity of the membrane is stronger, the Chinese patent medicine liquid medicine passes through the membrane, the density and the viscosity of the liquid medicine are larger, the time for the liquid medicine of unit volume to pass through the membrane is longer, namely, the retention time of the liquid medicine in the membrane is longer, effective components in the liquid medicine are easy to be absorbed by the membrane, the absorption of a patient to the medicine is not facilitated, meanwhile, after a large amount of effective components are absorbed in the membrane, the drug effect can be reduced, the recovery of the patient is not facilitated, the porosity of the membrane is reduced, the membrane flux is reduced too fast, after long-time infusion, the membrane flux is reduced, the infusion time is too long time, and the discomfort of the patient is easy to cause. For example, negative charges are hydroxyl, sulfonic acid group and the like, wherein the number of hydroxyl is positively correlated with the hydrophilicity of the membrane, for example, in the similar Shenmai injection, saponin substances are taken as effective medicine components, the structural formula of the saponin substances contains more hydroxyl, hydroxyl ionization can enable the saponin substances to be weakly electronegative, and when the negative charge density of the membrane is more than 20 x 10^-9mol/cm2Can ensure the hydrophilicity of the membrane, namely the membrane can be quickly wetted, when the negative charge density of the membrane is less than 55 x 10^ s-9mol/cm2While, the diaphragm pair can be loweredThe absorption of the effective components in the Chinese patent medicine liquid ensures the curative effect of the liquid medicine. Further, the smaller the pore diameter of the membrane, the larger the specific surface area of the membrane, and therefore, the pore diameter in the membrane cannot be too large or too small, and it is necessary to have a suitable pore.
Preferably, in the sulfone polymer microporous liquid stopper film, the ratio of the number of pores with the pore diameter of more than 6 μm measured by a PMI pore diameter tester to the total number of pores is 1-12%.
Holes with the aperture of more than 6 microns measured by PMI are defined as macropores, the ratio of the number of the macropores to the number of the holes cannot be too large, preferably 3-9%, otherwise, the larger the pore diameter of the macropores, the larger the number of the macropores, firstly, the smaller the surface tension between the Chinese patent medicine liquid and the membrane, the weaker the capillary phenomenon generated when the liquid passes through the membrane, and the lower the liquid stopping height of the membrane or the liquid stopping failure of the membrane is caused, and the membrane has no applicability; secondly, the larger the pore diameter of the macropores, the more the number of the macropores, the lower the filtering performance of the membrane; in addition, when the Chinese patent medicine liquid is stopped, large granular substances such as glass slag and the like at the fracture part of the bottle opening of an ampoule bottle can be found to exist in the Chinese patent medicine liquid, and the large pores can cause the glass slag not to be completely intercepted, so that the large granular substances such as the glass slag and the like have certain potential safety hazard after flowing into a human body along with the liquid medicine and can influence the liquid stopping performance of the membrane; meanwhile, the ratio of the number of the large holes to the whole number of the holes cannot be too small, when the number of the large holes is small, the flux of the membrane is reduced, the flow rate of the liquid medicine passing through the membrane is slowed, the infusion time of a patient is prolonged, and along with the increase of time, the flux attenuation speed of the membrane is high, so that the flow rate of the liquid medicine in the infusion process is unstable, and the situation that the flow rate is slower and slower possibly occurs, so that the discomfort or the psychological anxiety of the patient is caused.
Holes with the pore diameter of 2.5-6 μm measured by PMI are defined as mesopores, the ratio of the number of the mesopores to the number of the pores is preferably 85-95%, and excessive holes with the pore diameter of more than 6 μm measured by PMI easily cause large particle impurities such as glass slag in Chinese patent medicine liquid to pass through, thereby reducing the filtering precision of the membrane and having potential safety hazard to human health; therefore, holes with a pore diameter of more than 6 μm cannot account for too large a ratio as measured by PMI; holes with the aperture smaller than 2.5 mu m measured by PMI result in smaller flux of liquid medicine in unit time, especially larger density and viscosity of Chinese patent medicine liquid medicine are more adverse to the circulation of the Chinese patent medicine liquid medicine, and glass slag blocks the holes after the liquid medicine passes, so that the flux of the diaphragm is reduced, the circulation of the liquid medicine is adverse, and the flow rate of the liquid medicine is influenced, therefore, the holes with the aperture smaller than 2.5 mu m measured by PMI cannot account for too large ratio; the holes with the aperture of 2.5-6 μm measured by PMI can ensure the filtration precision of the membrane, and can ensure the slow flux attenuation of the membrane along with the extension of the infusion time.
Preferably, the first porous surface is provided with a plurality of first pores, and the average pore diameter of the first pores is 4-20 μm;
the second porous surface is provided with a plurality of second holes, and the average pore diameter of the second holes is 7-28 mu m.
The second porous surface is used as the liquid inlet surface of the Chinese patent medicine liquid, the first porous surface is used as the liquid outlet surface of the Chinese patent medicine liquid, the average pore diameter of the second porous surface is larger than that of the first porous surface, the larger pore diameter of the second porous surface is beneficial to the liquid medicine to rapidly enter the sulfone polymer microporous liquid stopping film, so that the sulfone polymer microporous liquid stopping film has larger flux, the flux of the liquid medicine is ensured to be stable, when the liquid medicine passes through the sulfone polymer microporous liquid stopping film, the filtering speed is higher, the filtering time of the liquid medicine can be shortened, the pore volume on the unit area is large, namely the carrying capacity is large, and fibers among gaps are few, namely the flow resistance is small; wherein the average pore diameter of the second porous surface is 7-28 μm, preferably 12-22 μm, and cannot be too large or too small, the filtering precision is low due to too large inner diameter of the pores, and the flux cannot be ensured due to too small inner diameter; the particle substances with the particle size of more than 28 mu m in the liquid medicine can not pass through the second porous surface, so that the prefiltering of the liquid medicine is completed, the filtering precision and the flux of the sulfone polymer microporous liquid stopping film are ensured to be stable, and the medication safety in practical application is ensured; meanwhile, the liquid medicine enters the sulfone polymer microporous liquid stopping film from the second porous surface, and due to the existence of holes with the average inner diameter of 7-28 mu m, the pore volume of the liquid inlet surface in unit area is large, the liquid medicine can be uniformly and quickly wetted on the whole sulfone polymer microporous liquid stopping film, and air existing in the sulfone polymer microporous liquid stopping film is prevented from entering a human body; the first porous surface is used as a liquid outlet surface, wherein the average pore diameter of the first porous surface is 4-20 microns, preferably 8-15 microns, and the first porous surface cannot be too large or too small, the inner diameter of the pores is too large, so that the filtering precision is low, the leakage risk exists, the flux cannot be ensured when the inner diameter is too small, and the particulate matters larger than 20 microns in the liquid medicine cannot pass through the second porous surface, so that the liquid medicine is filtered for multiple times, and the sulfone polymer microporous liquid stopping membrane disclosed by the invention is ensured to have higher filtering precision and stable flux, and the medication safety in practical application is ensured.
In addition, the first porous surface is the liquid outlet surface of the liquid medicine, so that the liquid medicine has a bearing effect on the whole of the sulfone polymer microporous liquid stopping membrane and the liquid medicine in the membrane, the average pore diameter of the first porous surface is not too large, the integral strength of the sulfone polymer microporous liquid stopping membrane is ensured, and the deformation resistance of the sulfone polymer microporous liquid stopping membrane at the liquid stopping end point is improved; wherein, the measurement mode of the average pore diameter of the membrane surface can be characterized by using a scanning electron microscope to perform morphology characterization on the membrane structure, then measuring by using computer software (such as Matlab, NIS-Elements and the like) or manually, and performing corresponding calculation; in the production of the membrane, various characteristics such as the pore size distribution in the direction perpendicular to the thickness of the membrane (the direction is a planar direction if the membrane is in the form of a flat sheet membrane; the direction is perpendicular to the radial direction if the membrane is in the form of a hollow fiber membrane) are substantially uniform and substantially uniform; the average pore size of the whole of the plane can be reflected by the average pore size of a partial region on the corresponding plane. In practice, the surface of the membrane can be characterized by an electron microscope to obtain a corresponding SEM image, and since the pores on the surface of the membrane are substantially uniform, a certain area, such as 1 μm, can be selected2(1 μm by 1 μm) or 25 μm2(5 μm multiplied by 5 μm), the specific area size is determined according to the actual situation, the pore diameters of all pores on the area are measured by corresponding computer software or manually, and then the average pore diameter of the surface is obtained by calculation; of course, the skilled person can also obtain the above parameters by other measuring means, which are only used as reference.
Preferably, the second porous surface has a pore density of second pores having a pore size of 10 to 35 μm of 15 to 70 pores/40000 μm2
And the ratio of the number of second holes with the aperture of 10-35 μm to the total number of second holes is not less than 70%;
on the first porous surface, the first pores with the pore diameter of 5-25 μm have a pore density of 6-50 pores/40000 μm2
The second porous surface is used as the liquid inlet surface of the membrane, the second holes with the pore diameter of 10-35 mu m are more suitable holes, the holes are uniformly distributed on the second porous surface of the sulfone polymer microporous liquid stopping membrane, the pore diameter is not too large, the flux of the membrane can be improved by the too large pore diameter, but the filtering precision of the membrane is reduced, particulate matters easily pass through the membrane, certain potential safety hazards exist, the surface tension of the liquid medicine and the surface of the membrane is reduced, the capillary phenomenon is weakened, and the liquid stopping height of the membrane is influenced; the aperture is not suitable to be too small, the flux of the membrane is reduced due to too small apertures, the flow rate of the liquid medicine is influenced, the infusion time is prolonged, and the flux of the membrane is attenuated quickly due to the fact that the Chinese patent medicine liquid with high viscosity and density is adsorbed in the membrane, so that the use of the membrane is influenced; the second holes have a suitable pore diameter, preferably 15-30 μm, and a suitable number and ratio of the second holes, preferably a pore density of 25-60 holes/40000 μm2(ii) a The ratio of the number of the holes to the number of the second holes is not less than 75%; the flux of the membrane is ensured to be large and stable enough and attenuated, and is still larger than 90% of the initial flux after a plurality of bottles of drops, and the membrane is ensured to have better hydrophilicity, liquid stopping performance and higher filtering precision, so that the sulfone polymer microporous liquid stopping membrane has excellent comprehensive performance.
The first porous surface is used as the liquid outlet surface of the membrane, the pore diameter is preferably 8-20 μm, the pore diameter of the first porous surface is smaller than that of the second porous surface, and the pore density is preferably 10-40 pores/40000 μm2(ii) a The first porous surface has a certain supporting effect on the whole membrane, and the second porous surface has a final filtering effect on the liquid medicine, so that the filtering precision of the membrane can be further improved.
Preferably, the porous body comprises two side areas and a middle area, the middle area is a liquid stopping layer, one side area of the porous body close to the second porous surface is a pre-filtering layer, one side of the porous body close to the first porous surface is a supporting layer, and the average pore size of the liquid stopping layer is smaller than that of the pre-filtering layer and that of the supporting layer; the thickness of the pre-filtering layer is at least larger than 15um, and the average pore size of the pre-filtering layer is 3-25 um.
In the membrane body structure of the sulfone polymer microporous liquid stopping membrane provided by the invention, a porous main body of the sulfone polymer microporous liquid stopping membrane comprises two side areas and a middle area in the thickness direction, wherein the middle area is a liquid stopping layer, one side area of the porous main body, which is close to a first porous surface, is a supporting layer, one side area of the porous main body, which is close to a second porous surface, is a pre-filtering layer, liquid medicine sequentially passes through the pre-filtering layer, the liquid stopping layer and the supporting layer, the average pore diameter of the liquid stopping layer is smaller than those of the pre-filtering layer and the supporting layer, holes in the pre-filtering layer can ensure higher pre-filtering precision, prevent particulate matters from flowing into the liquid stopping layer to influence the liquid stopping effect and ensure the flux of the liquid medicine, the holes in the supporting layer can improve the overall strength of the sulfone polymer microporous liquid stopping membrane, and can make the membrane more flat and prevent curling deformation; the holes in the liquid stopping layer can further ensure the filtering precision of the membrane, and meanwhile, due to the existence of the non-directional tortuous passage of the liquid stopping layer and the small pore diameter of the liquid stopping layer, the friction force of the liquid medicine in the passage of the liquid stopping layer is large, surface tension is generated between the liquid medicine and the surface of the passage of the liquid stopping layer, the surface tension enables the liquid medicine to be adhered in the liquid stopping layer, the surface tension is upward pulling force towards the liquid inlet surface, the liquid medicine below the liquid outlet surface is sucked, and liquid stopping is achieved; if the pore diameter of the liquid stopping layer is too large, the generated surface tension is small or no surface tension is generated, and liquid stopping cannot be realized.
The pre-filtering layer is used as the inflow side of the liquid medicine and has a main pre-filtering function on the liquid medicine; the pre-filtering layer also has a certain protection effect on the liquid stopping layer, and as some impurities with large particle size, such as glass slag, which is relatively sharp compared with other impurities, may exist in the Chinese patent medicine, if the pre-filtering layer does not exist or the thickness of the pre-filtering layer is too small, the glass slag is easily contacted with the liquid stopping layer in the liquid stopping film, the glass slag can scratch or even damage the liquid stopping layer, and the liquid stopping layer cannot perform a good liquid stopping effect; the thickness of the pre-filtering layer is at least larger than 15 micrometers, the average pore size of the pre-filtering layer is 3-25 micrometers (the thickness of the pre-filtering layer is preferably 15-35 micrometers, and the average pore size of the pre-filtering layer is preferably 8-20 micrometers), and by controlling the thickness and the pore size of the pre-filtering layer, the integral flux of the membrane is ensured, the pre-filtering effect is achieved, the liquid stopping layer can be protected, and the influence of relatively sharp impurities such as glass slag is avoided.
Preferably, the thickness of the sulfone polymer microporous liquid stopping film is 50-150 μm, and the PMI average pore diameter is 3-5 μm; the porosity is 70-98%.
The thickness of the sulfone polymer microporous liquid stopping membrane is micron-sized, preferably 90-120 mu m, and the whole thickness of the membrane is thinner, so that the membrane is easier to be arranged in a liquid stopping device, the flow of Chinese patent medicine liquid is facilitated, and the flow rate of the liquid medicine is increased; when the thickness of the sulfone polymer microporous liquid stopping film is too small, the strength of the film is smaller; meanwhile, as the filtering time is short, effective filtering cannot be carried out; when the thickness of the sulfone polymer microporous liquid stopping film is too large, the filtration time is too long, and the filtration efficiency is influenced; therefore, when the sulfone polymer microporous liquid stopping membrane has proper thickness, on one hand, the mechanical strength is high, on the other hand, effective filtration can be carried out, and the filtration efficiency is high; the sulfone polymer microporous liquid stopping membrane has high porosity, preferably 85-98%, so that high flux of the sulfone polymer microporous liquid stopping membrane is further ensured.
Preferably, the liquid stopping layer is of a symmetrical structure, and the pore size of the side, close to the pre-filtering layer, of the liquid stopping layer is basically the same as the pore size of the side, close to the supporting layer, of the liquid stopping layer;
the average pore diameter of the liquid stopping layer is 1-13um, and the thickness of the liquid stopping layer is 10-40 um; the average pore diameter of the supporting layer is 2-18um, and the thickness is 20-60 um.
Preferably, the thicknesses of the liquid stopping layer and the support layer are as follows in sequence: 15-30 μm and 30-50 μm, wherein the support layer is used as the outflow side of the liquid medicine, has a supporting function on both the pre-filter layer and the liquid stopping layer, and has a thickness slightly larger than that of the pre-filter layer and the liquid stopping layer so as to ensure the integral strength of the sulfone polymer microporous liquid stopping membrane and prevent the membrane from being damaged; the thickness of the liquid stopping layer is relatively thin, which means that the smaller the number of the holes of the liquid stopping layer is, the smaller the hole diameter of the liquid stopping layer is enough to achieve the liquid stopping effect, and preferably, the average hole diameters of the liquid stopping layer and the supporting layer are sequentially as follows: 3-10um, 5-15 um.
Preferably, the surface energy of the sulfone polymer microporous liquid stopping film is 80-120 mN/m; the initial contact angle of the saturated saline drop to the sulfone polymer microporous liquid stop film is 55-75 degrees, and the time for the contact angle to be changed into 0 degree is 2-10 s; the work of adhesion was 100J/m2-170J/m2
The sulfone polymer microporous liquid stopping membrane provided by the invention has higher hydrophilicity and high wetting speed, and the hydrophilicity is stronger when the test liquid is saturated saline water; the surface energy of the membrane is preferably 90-115 mN/m; the surface energy is not limited to a certain surface of the sulfone polymer microporous liquid stop film, and can be a first porous surface or a second porous surface; by adopting saturated saline solution as a test solution, the surface energy of the saturated saline solution is greater than that of water, the surface energy of the saturated saline solution is 81.4mN/m, and the surface energy of the water is 72.8 mN/m; the hydrophilicity of the sulfone polymer microporous liquid stopping film can be embodied more accurately; one of the most common solvents in infusion is saline, which is more reasonable and accurate compared with a liquid stopping membrane and can further embody the hydrophilicity of the microporous liquid stopping membrane of the sulfone polymer; the volume of a drop of saturated salt solution selected by the test solution is about 0.04-0.05ml, the area of the selected sulfone polymer microporous liquid stop film can at least completely absorb a drop of saturated salt solution, the drop of saturated salt solution is dropped on the first porous surface or the second porous surface of the sulfone polymer microporous liquid stop film until the contact angle is changed to 0 degrees, namely the saturated salt solution is completely wetted on the sulfone polymer microporous liquid stop film, and the used time is not more than 15s, preferably not more than 10 s; the contact angle can be accurately measured by adopting a contact angle tester, the surface energy of the sulfone polymer microporous liquid stopping membrane is higher, and the time that the contact angle edge is 0 ℃ when saturated salt water is dropped on the membrane is short; the sulfone polymer microporous liquid stopper film has excellent wetting performance, can quickly wet saturated saline, and can be understood that liquid medicine can quickly wet a membrane to prevent bubbles from remaining in the membrane and flowing into a patient during infusion; the utility model has higher practicability when facing the emergency transfusion or the emergency rescue of the patient.
The sulfone polymer microporous liquid stopping film has the advantages that the sulfone polymer microporous liquid stopping film meets the liquid stopping effect, the flowing speed is high, namely, the hydrophilicity is high, the initial contact angle of saturated saline water when the saturated saline water drops to the sulfone polymer microporous liquid stopping film is the average value of the left contact angle and the right contact angle of the saturated saline water and the sulfone polymer microporous liquid stopping film, and the shorter the time for changing the contact angle to 0 degrees is, the higher the wettability of the sulfone polymer microporous liquid stopping film is represented. Work of adhesion is defined as the area of 1cm2The more the solid-liquid interface is pulled, the less the liquid is peeled off from the solid surface, the more the solid is hydrophilic, and the preferred work of adhesion between the saturated salt solution and the sulfone polymer microporous liquid stopping film is 140J/m2-170J/m2Thus further showing that the saturated saline solution has strong affinity with the membrane and can quickly wet the membrane.
Preferably, the IPA complete foaming point of the sulfone polymer microporous liquid stopping film is 9-16KPa, and the IPA initial foaming point is 6-10 KPa; the ratio of the initial bubble point of the IPA to the complete bubble point of the IPA is (0.55-0.85): 1.
the bubble point is an important performance characteristic of the membrane, and the application range of the liquid stopping membrane is greatly influenced by the bubble point; the methods of bubble point testing are well known in the art and the procedures for such testing are explained in detail in, for example, ASTM F316-70 and ANS/ASTM F316-70 (re-approved in 1976), which are incorporated herein by reference. The test liquid used in the invention is IPA (isopropyl alcohol); the bubble point is divided into an initial bubble point and a complete bubble point; when the middle of the liquid stopping film starts to continuously bubble, reading the pressure at the moment as an initial bubble point; when the membrane was fully bubbled, the pressure at that time was read as the point of full bubbling.
Therefore, the initial bubble point and the complete bubble point react the pore diameter structure of the sulfone polymer microporous liquid stopping film from another angle, the initial bubble point reacts the maximum pore diameter in the film, the smaller the initial bubble point is, the larger the maximum pore diameter in the film is, namely a certain number (though the number is smaller) of holes with larger pore diameters exist in the film, and the existence of the holes can further accelerate the speed of the liquid medicine for completely wetting the film, but the weaker the capillary phenomenon generated when the liquid medicine enters the film is, and the lower the liquid stopping height is; in addition, the existence of the large-aperture holes can cause the low filtration precision of the membrane, and large-particle substances can easily pass through the membrane, and the large-particle substances can cause harm to the body of a patient; on the contrary, the larger the initial bubble point is, the smaller the maximum pore size is, and it can be understood that all the pore sizes in the membrane are smaller at the moment, and at the moment, the capillary phenomenon generated when the liquid medicine enters the membrane is strong, and the liquid stopping height is higher; however, due to the existence of the excessively small aperture, the structure of the diaphragm is compact, the speed of the liquid medicine wetting the diaphragm is low, the initial liquid inlet speed and the initial liquid outlet speed of the diaphragm are inconsistent, the air in the diaphragm is discharged slowly or cannot be completely discharged, and certain potential safety hazards exist; and the flux of the membrane is low.
The minimum pore diameter in the complete bubble point reaction membrane is larger, the minimum pore diameter is smaller, and the proper complete bubble point of the membrane ensures that the membrane has higher interception efficiency; therefore, the ratio of the IPA initial bubble point to the IPA complete bubble point of the sulfone polymer microporous liquid stopping film is (0.55-0.85): 1, preferably (0.6-0.8): 1; the pore diameter in the membrane is ensured to be relatively uniform, no pores which are particularly large and pores which are particularly small are existed, and the pore diameter is relatively uniform, so that the entrapment efficiency of the sulfone polymer microporous liquid stopping membrane is ensured to be high, and the complete wetting speed is high and uniform.
Preferably, the average fiber diameter of the porous structure formed in the support layer is larger than the average fiber diameter of the porous structure formed in the liquid stop layer and the pre-filter layer; the average fiber diameters of porous structures formed in the pre-filtering layer, the liquid stopping layer and the supporting layer are 1-10 microns, 0.8-7 microns and 2-12 microns in sequence; the fibers in the porous main body are all in a strip-shaped structure; the fiber structure can improve the overall mechanical performance of the membrane, wherein the average fiber diameter of the supporting layer is slightly thicker than that of the pre-filtering layer and the liquid stopping layer, and good supporting strength can be provided for the pre-filtering layer and the liquid stopping layer.
The main body of the sulfone polymer microporous liquid stopping membrane is internally provided with a plurality of non-directional tortuous passages, each passage is arranged along the thickness direction of the membrane, each passage is a flow path of the liquid medicine, the fibers in the main body are of strip structures, and each passage is formed by the strip fiber structures, so that a flow channel of the liquid medicine is closer to turbulent flow, the contact probability of the liquid medicine and the fibers is increased, the filtration efficiency is improved, the interception efficiency is ensured, and the liquid stopping membrane is ensured to have higher flux; it will be appreciated that the fibrous structures are integrally connected to one another, e.g., integrally formed, without the need for additional adhesives or the like to interconnect them, and that the network-like fibers cannot be separated from one another unless torn by an external force.
The average fiber diameter of the fibers in each area of the sulfone polymer microporous liquid stopping film is different, wherein the support layer has larger average fiber diameter and plays a strong supporting role; the existence of the fiber with larger diameter can greatly improve the mechanical strength of the membrane, and the existence of the fiber with smaller diameter further improves the mechanical strength of the membrane, so that the membrane has larger tensile strength and elongation at break; the larger fiber structure is beneficial to intercepting the particulate matters with larger particle sizes, the smaller fiber structure is beneficial to intercepting the particulate matters with smaller particle sizes, and finally the fine particulate matters can be intercepted, so that the structure can greatly improve the effective interception rate of the liquid stopping film on the particulate matters, and the filtering precision is high; meanwhile, due to the existence of the fiber layer with larger diameter, the flux of the liquid stopping film is larger, the filtering time is shorter, the time cost is lower, and the economic benefit is higher; during infusion, the patient can adjust the liquid medicine speed according to self health condition, and because the flux of ending the liquid film is great, make the liquid medicine velocity of flow can adjust real-time change according to the patient, the time error is little.
Wherein the fibers within each layer are substantially uniformly distributed, and although the degree of thickness is not exactly the same between the fibers in the network, the fibers are uniform as a whole in each layer, show no significant ascending or descending regularity, and have no interface with a significant abrupt change in average fiber diameter between the adjacent two layers. The average fiber diameter can be measured by computer software (such as Matlab, NIS-Elements and the like) or manually after the morphology characterization of a membrane structure is carried out by using a scanning electron microscope, and then the average value is calculated; in addition, the thickness of the whole polymer liquid-stopping film and the thickness of the three-layer structure in the polymer liquid-stopping film can also be measured by the method; it will be appreciated that the above parameters may also be obtained by other measurement means by a person skilled in the art.
Preferably, the tensile strength of the sulfone polymer microporous liquid stopping membrane is 3-10MPa, the breaking elongation is 30-60%, and the water flux is 150--1*cm-2The interception efficiency of the sulfone polymer microporous liquid stopping film to impurity particles with the particle size not less than 5 mu m is more than 90%.
The sulfone polymer microporous liquid stopping membrane has excellent mechanical performance, ensures that the membrane cannot be damaged and fiber floccules cannot fall off under the condition of long-time use, ensures that the membrane has good flux when in use due to the structure in the membrane, has basically consistent liquid inlet speed and liquid outlet speed, and has higher practicability; important indexes for evaluating the mechanical strength of the liquid stopping film are the tensile strength and the elongation at break of the liquid stopping film; under certain conditions, the larger the tensile strength of the liquid stopping film is, the better the mechanical strength of the liquid stopping film is; tensile strength refers to the ability of a film to withstand parallel stretching; when the film is tested under a certain condition, the film sample is acted by a tensile load until the film sample is damaged, and the tensile strength and the elongation at break of the film can be calculated according to the maximum tensile load corresponding to the damage of the film sample, the change of the size (length) of the film sample and the like; tensile strength, elongation at break, can be measured by a universal tensile tester, tensile strength testing methods are well known in the art, for example, tensile strength testing procedures are explained in detail in ASTM D790 or ISO 178; the tensile strength of the liquid stopping film is 3-10 MPa; the elongation at break is 30-60%, which shows that the liquid stopping film has higher tensile strength and elongation at break, better mechanical property and higher industrial practical value, and can completely meet the market demand.
Flux of permeationThe permeation rate, flux for short, refers to the amount of substance that the liquid stop membrane passes through per unit membrane area in a single-unit time under a certain working pressure during the separation process; the flux reflects the speed of the filtration; the higher the flux, the faster the filtration rate of the membrane; the flux of the sulfone polymer microporous liquid stopping membrane in the invention is 150-260mL-1*cm-2The higher flux indicates that the filtering speed of the liquid stopping membrane is higher, so that the speed of hanging the infusion can be adjusted, and the infusion set is suitable for patients with various conditions; when the conditions allow, the drip hanging speed can be properly accelerated, and the time of the patient is saved; and when the interception efficiency is ensured, the fluid can rapidly pass through the liquid stop membrane, the time cost is lower, and the economic benefit is higher.
The sulfone polymer microporous liquid stopping film provided by the invention is based on the Chinese medicine industry standard YY
0770.1-2009 for medical infusion and injection device, the content of dissolved matter, fluorescence matter, and the falling amount of particles meet the standard.
A preparation method of a sulfone polymer microporous liquid stopping film comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 5-20 parts of sulfone polymer, 40-75 parts of first organic solvent and 6-25 parts of hydrophilic additive;
s2: placing the liquid film in air environment at 10-40 deg.C, and adjusting the absolute humidity to 15gH2O/kg-35g H2Blowing O/kg air flow onto the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.4-0.8m/s, and the duration is 8-25 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 10-40 ℃, and the re-phase solidification time is 30-150 s; the coagulating bath is a mixture of a second organic solvent and water; wherein the second organic solvent can be mutually soluble with water and the first organic solvent, and the volume of the second organic solvent is 5-25% of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.05-1.5 times of area, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
Preferably, the sulfone polymer comprises at least one of polyethersulfone, polysulfone, and polyarylsulfone;
the hydrophilic additive comprises one or a combination of polyvinyl alcohol, polyethylene glycol, polyethyleneimine and polyvinylpyrrolidone;
the first organic solvent is at least one of dimethyl sulfoxide, dimethylformamide, caprolactam, N-ethyl pyrrolidone, dimethylacetamide and N-methyl pyrrolidone;
the second organic solvent is at least one of dimethyl sulfoxide, caprolactam, N-methyl pyrrolidone, N-ethyl pyrrolidone, dimethylformamide, dimethylacetamide, trimethyl phosphate, triethyl phosphate and r-butyrolactone.
In the method, firstly preparing a casting solution, wherein the casting solution comprises a sulfone polymer, a first organic solvent and a hydrophilic additive; the sulfone polymer is at least one of polyether sulfone, polysulfone and polyarylsulfone, and the polymer has excellent oxidation resistance, thermal stability and mechanical property, so that the mechanical property of a formed film is excellent, various processing treatments can be met, and the industrial value is high; meanwhile, the water-based anti-bacterial film has good hydrophilicity and is suitable for being used as a liquid-stopping film; wherein the first organic solvent is at least one of dimethyl sulfoxide, dimethylformamide, caprolactam, N-ethyl pyrrolidone, dimethylacetamide and N-methyl pyrrolidone, and is used for fully dissolving the sulfone polymer material, so as to form a uniform and stable casting solution (homogeneous system); the hydrophilic additive is the combination or one of polyvinyl alcohol, polyethylene glycol, polyethyleneimine and polyvinylpyrrolidone, and can effectively control the viscosity of the system, inhibit the formation of macropores in a liquid film in a phase splitting process and effectively improve the stability of the flux of the film; in addition, the hydrophilicity of the formed film can be greatly improved, so that the formed film has higher hydrophilicity and is suitable for being used as a liquid stopping film; the proportion of the sulfone polymer, the first organic solvent and the hydrophilic additive is adjusted, so that the casting solution has proper viscosity, and the viscosity of the casting solution can have great influence on the structure and the performance of the finally formed filter membrane, such as the pore diameter, the thickness, the flow rate and the like of the filter membrane; thereby ensuring that the finally prepared sulfone polymer microporous liquid stopping membrane has proper thickness and ideal membrane pore structure and pore size;
casting the prepared casting solution on a carrier to form a liquid film; the casting solutions of the present invention may be cast manually (e.g., by pouring, casting, or spreading by hand on a casting surface) or automatically (e.g., poured or otherwise cast on a moving bed); a variety of apparatus known in the art can be used for casting. Casting equipment includes, for example, mechanical coaters, including doctor blades, or spray/pressurized systems. As is known in the art, a variety of casting speeds are suitable, such as casting speeds of about 2 to 6 feet per minute (fpm), and the like, as the case may be;
casting the self-made casting film liquid on a carrier to form a liquid film; then placing the liquid film at an absolute humidity of 15-35g H2In a moist environment of O/kg, the liquid film can be induced to carry out pre-phase separation; under such humidity conditions, the formation of coarse fibers of the support layer is favoured; in particular, the process of immersing the liquid film and the carrier into the curing liquid is beneficial to the formation of the internal various layer structures: simultaneously blowing air flow with the flow velocity of 0.4-0.8m/s to the surface of the liquid film, wherein the pre-phase separation time is 8-25 s; thus, the liquid film can form a first porous surface and a supporting layer in a pre-phase separation manner under the action of wet air flow, and a certain number of holes with proper pore size are formed on the first porous surface; the absolute humidity and the flow velocity of the airflow are related to the pore size and the number of the holes on the first porous surface.
The first porous surface and the supporting layer are formed on the liquid film, when the liquid film is completely immersed in the coagulating bath, the coagulating bath can only enter the film body through the first porous surface because the coagulating bath cannot penetrate through one side of the carrier, at the moment, the holes formed by earlier-stage phase separation in the supporting layer can enable the solidifying liquid to smoothly pass through until the corresponding region before the liquid stopping layer is formed, and then the concentration of the coagulating bath in the corresponding region before the liquid stopping layer is formed can be quickly increased, and the region is subjected to phase separation solidification to form the liquid stopping layer in a short time; the shorter the phase separation time is, the smaller the average pore diameter is, so that a liquid stopping layer with small average pore diameter is formed; it is emphasized that, due to the greater humidity of the gas flow controlled in S2, the larger average pore size formed at the first porous surface will facilitate the rapid passage of the coagulation bath and thus the formation of a liquid stop layer; meanwhile, the average pore size of the first porous surface and the support layer also has great influence on the average pore size of the liquid stopping layer, the average pore size of the pre-filtering layer and the average pore size of the second porous surface;
along with the lapse of soaking time, the coagulating bath enters a corresponding region before the pre-filtering layer is formed, and further gradually diffuses towards the direction of the carrier, and the concentration of the coagulating bath always has a certain gradient, namely the concentration of the coagulating bath close to one side of the first porous surface is greater than that of the coagulating bath close to one side of the carrier, so that the water concentration of the solidified liquid in the corresponding region before the pre-filtering layer is formed is relatively low, the phase separation time is long, and finally the pre-filtering layer with relatively large average pore diameter and the second porous surface with relatively large average pore diameter are formed;
wherein the coagulating bath is a mixture of a second organic solvent and water, the water is a non-solvent, the second organic solvent can be mutually soluble with the water and also can be mutually soluble with the first organic solvent, and the volume of the second organic solvent is 5-25% of the volume of the mixture, wherein the shorter the phase separation time is, the smaller the pore diameter of the formed pores is, and thus the smaller the flux of the membrane is; less second organic solvent can reduce the phase separation speed and relatively prolong the phase separation time, so that more holes with proper pore diameters are formed, the sulfone polymer microporous liquid stopping film has enough flux, and the flux attenuation of the film is slower along with the prolonging of the Chinese patent medicine drip injection time.
Then air-drying to form a solid film, wherein the air-drying can be natural air-drying or air-drying by using a machine such as an electric fan; then stretching the solid film to 1.05-1.5 times of the original area; the stretching mode can form unidirectional stretching through the speed difference of the front roller and the rear roller, and can also be obtained by carrying out bidirectional stretching on the solid film; after the solid film is stretched, the mechanical strength of the solid film is improved, and the solid film becomes a tough film; and shaping after stretching is finished, wherein the shaping can be heat shaping, so that the sulfone polymer microporous liquid stopping membrane with an ideal membrane structure is obtained, has stronger hydrophilicity, and can be quickly wetted by deionized water, saturated salt water and other liquids, thereby further ensuring the health of a patient.
The application of the sulfone polymer microporous liquid stopping film in a liquid stopping device, wherein the liquid stopping device comprises a shell, the sulfone polymer microporous liquid stopping film arranged in the shell and a side cover sealed on the shell, a medicine inlet and a medicine outlet are arranged in the vertical direction of the shell, the sulfone polymer microporous liquid stopping film is arranged in the shell and divides the shell into a liquid inlet cavity and a liquid outlet cavity, the medicine inlet is communicated with the liquid inlet cavity, and the medicine outlet is communicated with the liquid outlet cavity; the liquid medicine enters the liquid inlet cavity from the medicine inlet, sequentially flows to the liquid outlet cavity through the second porous surface and the first porous surface of the sulfone polymer microporous liquid stopping film, and flows out from the medicine outlet.
The sulfone polymer micropore liquid stopping film is arranged in the liquid stopping device and used for stopping the injection liquid of the plant extraction liquid with higher density and viscosity, the flux of the sulfone polymer micropore liquid stopping film is larger, the infusion time is increased, the flux attenuation of the film is slowed down, the condition that the flow rate of the liquid medicine is slower and slower after the patient conducts infusion for a long time is avoided, the infusion time of the patient is slowed down, the flow rate of the liquid medicine can be adjusted and changed at any time by the patient according to the self condition, the time delay when the flow rate of the liquid medicine is changed is reduced, and the liquid stopping device has higher applicability.
Preferably, the second porous surface is a liquid inlet surface, and the first porous surface is a liquid outlet surface.
Compared with the prior art, the invention has the beneficial effects that: the sulfone polymer microporous liquid stopping membrane provided by the technical scheme has a more optimized membrane body structure, and simultaneously has more optimized comprehensive performance, enough and stable flux, slow flux attenuation, high filtration precision, excellent and stable liquid stopping performance, larger flux and the like; the preparation method provided by the technical scheme can conveniently, quickly and effectively prepare and obtain the sulfone polymer microporous liquid stopping film; the liquid stopping device provided by the technical scheme can be filled with liquid medicine quickly, the flux of the liquid stopping device is increased, the filtering precision of the liquid stopping device is further improved, and the liquid stopping device is more applicable.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a second porous surface of a sulfone polymer microporous liquid stopper film prepared in example 1 of the present invention, wherein the magnification is 500;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the first porous surface of the sulfone polymer microporous liquid stopper film prepared in example 1 of the present invention, wherein the magnification is 500;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a second porous surface of a sulfone polymer microporous liquid stopper film prepared in example 3 of the present invention, wherein the magnification is 500;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the first porous surface of the sulfone polymer microporous liquid stopper film prepared in example 3 of the present invention, at 500 magnification;
FIG. 5 is a Scanning Electron Microscope (SEM) image of a second porous surface of a sulfone polymer microporous liquid stopper film prepared in example 5 of the present invention, wherein the magnification is 500;
FIG. 6 is a Scanning Electron Microscope (SEM) image of the first porous surface of the sulfone polymer microporous liquid stopper film prepared in example 5 of the present invention, at 500 magnification;
FIG. 7 is a schematic view of a sulfone polymer microporous liquid stopping membrane bubble point test device according to the present invention;
FIG. 8 is a schematic view of the filtration precision testing apparatus for the sulfone polymer microporous liquid stopper film of the present invention;
FIG. 9 is a schematic structural diagram of a liquid stopper according to the present invention;
fig. 10 is a sectional view of the liquid stopper provided by the present invention.
Description of the reference numerals
1. A housing; 11. a medicine inlet; 12. a medicine outlet; 2. a sulfone polymer microporous liquid stop membrane; 3. a side cover; 4. a support; 5. supporting ribs; 51. a recess.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, raw materials and equipment for preparing the liquid-repellent film were commercially available, unless otherwise specified. The method comprises the following steps of preparing a liquid stopping film by using a steel belt casting machine, and characterizing the structural morphology of the liquid stopping film by using a scanning electron microscope with the model number of S-5500 provided by Hitachi.
Example 1
This example 1 provides a sulfone polymer microporous fluid stop membrane, prepared by the following method: the method comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 8 parts of polyether sulfone, 48 parts of dimethyl sulfoxide and 12 parts of polyvinyl alcohol;
s2: placing the liquid film in air at 35 deg.C, and adjusting the absolute humidity to 15g H2Blowing O/kg air flow onto the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.45m/s, and the duration is 24 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 23 ℃, and the re-phase solidification time is 147 s; the coagulating bath is a mixture of dimethyl sulfoxide and water; the volume of the dimethyl sulfoxide is 24% of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.42 times, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
Example 2
This example 2 provides a sulfone polymer microporous fluid stop membrane, prepared by the following method: the method comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 12 parts of polysulfone, 60 parts of dimethylformamide and 15 parts of polyethylene glycol;
s2: placing the liquid film in air environment with temperature of 28 deg.C, and then placing the liquid film at absolute humidity of 28g H2Blowing O/kg air flow onto the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.65m/s, and the duration is 12 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 10 ℃, and the re-phase solidification time is 72 s; the coagulating bath is a mixture of dimethylformamide and water; the volume of the N-methyl pyrrolidone is 9 percent of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.5 times, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
Example 3
This example 3 provides a sulfone polymer microporous fluid stop membrane, prepared by the following method: the method comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 15 parts of polyarylsulfone, 62 parts of N-ethyl pyrrolidone and 24 parts of polyethyleneimine;
s2: placing the liquid film in air at 15 deg.C, and adjusting the absolute humidity to 19g H2Blowing O/kg air flow onto the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.52m/s, and the duration is 19 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 14 ℃, and the re-phase solidification time is 127 s; the coagulating bath is a mixture of N-methyl pyrrolidone and water; the volume of the N-methyl pyrrolidone is 17 percent of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.21 times, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
Example 4
This example 4 provides a sulfone polymer microporous liquid stopper film, prepared by the following method: the method comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 5 parts of polyether sulfone, 49 parts of dimethylacetamide and 8 parts of polyvinylpyrrolidone;
s2: placing the liquid film in air environment with temperature of 10 deg.C, and then placing the liquid film at absolute humidity of 32g H2Blowing O/kg air flow onto the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.71m/s, and the duration is 10 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 28 ℃, and the re-phase solidification time is 59 s; the coagulating bath is a mixture of dimethylformamide and water; wherein the volume of dimethylformamide is 7% of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.11 times, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
Example 5
This example 5 provides a sulfone polymer microporous fluid stop membrane, prepared by the following method: the method comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 17 parts of polyether sulfone, 75 parts of dimethylacetamide and 21 parts of polyvinylpyrrolidone;
s2: placing the liquid film in air at 19 deg.C, and adjusting the absolute humidity to 35g H2Blowing O/kg air flow onto the surface of the liquid film to pre-split the liquid film, wherein the relative speed between the air flow and the liquid film is 0.8m/s, and the duration is 8 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 39 ℃, and the re-phase solidification time is 30 s; the coagulating bath is a mixture of dimethylacetamide and water; wherein the volume of the dimethylacetamide is 5% of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.35 times, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
Example 6
This example 6 provides a sulfone polymer microporous fluid stop membrane, prepared by the following method: the method comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 20 parts of polyarylsulfone, 72 parts of caprolactam and 25 parts of polyethyleneimine;
s2: placing the liquid film in air at 40 deg.C, and adjusting the absolute humidity to 25g H2Blowing O/kg air flow onto the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.69m/s, and the duration is 15 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 40 ℃, and the re-phase solidification time is 88 s; the coagulating bath is a mixture of caprolactam and water; wherein the volume of caprolactam is 11% of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.27 times, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
Example 7
This example 7 provides a sulfone polymer microporous liquid stopper film, prepared by the following method: the method comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 10 parts of polysulfone, 52 parts of N-ethyl pyrrolidone and 13 parts of polyethylene glycol;
s2: placing the liquid film in air environment with temperature of 24 deg.C, and then placing the liquid film at absolute humidity of 17g H2O/kg ofBlowing air flow to the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.41m/s, and the duration is 22 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 35 ℃, and the re-phase solidification time is 132 s; the coagulating bath is a mixture of N-methyl pyrrolidone and water; wherein the volume of the N-methyl pyrrolidone is 21 percent of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.09 times, cleaning in pure water, and finally drying to obtain the sulfone polymer microporous liquid stopping membrane.
Example 8
This example 8 provides a sulfone polymer microporous fluid stop membrane, prepared by the following method: the method comprises the following steps:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 13 parts of polyarylsulfone, 58 parts of dimethyl sulfoxide and 18 parts of polyvinylpyrrolidone;
s2: placing the liquid film in air environment with temperature of 32 deg.C, and then placing the liquid film at absolute humidity of 21g H2Blowing O/kg air flow onto the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.58m/s, and the duration is 17 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 17 ℃, and the re-phase solidification time is 101 s; the coagulating bath is a mixture of gamma-butyrolactone and water; wherein the volume of gamma-butyrolactone is 15% of the volume of the mixture;
s4; and (3) stretching the raw membrane by 1.3 times, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
Comparative example 1
Any common liquid stopping membrane in the market is selected, and tested by a PMI pore diameter tester, the ratio of the number of holes with the PMI pore diameter not more than 2.5 mu m to the total number of the holes is 43 percent, and the ratio of the number of holes with the PMI pore diameter more than 6 mu m to the total number of the holes is 10 percent.
Comparative example No. two
Any common liquid stopping membrane in the market is selected, and tested by a PMI pore diameter tester, the ratio of the number of holes with the PMI pore diameter not more than 2.5 mu m to the total number of the holes is 5%, and the ratio of the number of holes with the PMI pore diameter more than 6 mu m to the total number of the holes is 39%.
First, structural characterization
The performance characteristics of the above examples and the comparative examples are shown in Table 1
TABLE 1
Figure BDA0003475967210000271
The thickness and porosity of the sulfone polymer microporous liquid-stop film, the thickness of each layer, the average pore diameter and the average fiber diameter of each layer were measured by using the scanning electron microscope for the morphological characteristics of the longitudinal sections of the sulfone polymer microporous liquid-stop films obtained in each example and comparative example, as shown in table 2.
TABLE 2
Figure BDA0003475967210000281
Second, flux test
The same specifications (1 x 1 cm) as those of the comparative examples were selected from the above examples2) The sulfone polymer microporous liquid stopper film of (a); the flux of the vegetal extract injection, the western medicine injection and water with the same volume passing through the membrane is measured, and the specific test method comprises the following steps: when other conditions are the same, firstly measuring the initial flux of the membrane by a certain volume of water, then passing the same volume of test liquid through the membrane, and then passing the water through the membrane to measure the final flux; the test solutions were: respectively 50mL of the ophioglossum distichum solution, 50mL of the ophioglossum distichum solution after being diluted by 5 times, 50mL of the Clary injection after being diluted by 5 times, 50mL of the glucose solution and 50mL of the water.
The membrane flux is calculated as follows:
the formula for calculating the membrane flux (J) is: j ═ V/(T × a) formula wherein:
j- -Membrane flux Unit: mL/min-1/cm-2(ii) a V- -sample volume (ml); t- -sample time (min); a- -effective area of the film (cm)2)
TABLE 3
Figure BDA0003475967210000291
Third, performance test
And (3) testing the filtering precision: the membranes obtained in each example were tested for their efficiency of interception.
Experimental equipment: a Tianjin Roots particle counter KB-3; preparation of the experiment: the experimental set-up was assembled as per fig. 9, ensuring the set-up was clean, and the set-up was rinsed with ultra-pure water; a sample with the diameter of 47mm is taken and is arranged in the butterfly filter, and the air tightness of the assembled filter is ensured to be good.
The experimental steps are as follows: pouring the challenge liquid into a storage tank, paying attention to the exhaust of the butterfly filter, pressurizing to 10kPa, and taking the filtrate at the downstream of the butterfly by using a clean bottle; the number of particles in the filtrate and stock solutions was measured using a particle counter.
Intercepting efficiency:
Figure BDA0003475967210000301
in the formula: eta-type-interception efficiency,%; n 0-number of particles in stock solution, average of 5 groups of counts; n 1-number of particles in filtrate, average of 5 groups of counts.
The interception efficiency test: the filtration precision of the sulfone polymer microporous liquid stopping membrane prepared in the examples 1 to 8 is more than 95 percent for 5 mu m impurity particles; the liquid-stopping membrane of comparative example 1 had a filtration accuracy of 98% for 5 μm impurity particles; the liquid-stopping membrane of comparative example 2 had a filtration accuracy of 72% for 5 μm impurity particles.
Bubble point test
Initial bubble point of water and complete bubble point of water of test sample (test device as figure 8)
The experimental steps are as follows:
the method comprises the following steps: and closing the air pressure regulator, opening the air pressure regulator to enable the pressure to be higher than the tested pressure, taking out the wetted sulfone polymer microporous liquid stopping membrane to be tested, and installing the wetted sulfone polymer microporous liquid stopping membrane on a filtering device.
Step two: the reservoir was filled with 80% of the test solution, the air pressure was increased, and the pressurization was stopped when about 80% of the bubble point was reached. It was confirmed that the sulfone polymer microporous liquid-stop membrane in the reservoir had not foamed at this time.
Step three: slowly increasing the pressure, and reading the pressure when the middle of the sulfone polymer microporous liquid stopping film begins to continuously bubble, wherein the pressure is used as an initial bubble point. Continuously increasing the pressure, when the sulfone polymer microporous liquid stopping film is completely foamed, reading the pressure at the moment, and taking the pressure as the maximum bubble point
Note that: typically, bubbles emerge from near the center of the sulfone polymer microporous liquid stopper film.
TABLE 4
Figure BDA0003475967210000311
As can be seen from the table, the sulfone polymer microporous liquid stopping membrane prepared by the invention has larger flux and complete bubble point, and is suitable for the field of liquid stopping medical treatment.
The invention also provides an application of the sulfone polymer microporous liquid stopping film in a liquid stopping device, the liquid stopping device comprises a shell 1, a sulfone polymer microporous liquid stopping film 2 arranged in the shell 1 and a side cover 3 sealed on the shell 1, a medicine inlet 11 and a medicine outlet 12 are arranged in the vertical direction of the shell 1, the sulfone polymer microporous liquid stopping film 2 is arranged in the shell 1 and divides the shell 1 into a liquid inlet cavity and a liquid outlet cavity, the medicine inlet 11 is communicated with the liquid inlet cavity, and the medicine outlet 12 is communicated with the liquid outlet cavity; the liquid medicine enters the liquid inlet cavity from the medicine inlet 11, sequentially flows to the liquid outlet cavity through the second outer surface and the first outer surface of the sulfone polymer microporous liquid stopping film 2, and flows out from the medicine outlet 12.
Specifically, the inside of the shell 1 is provided with a bracket 4 forming a seal with the inner wall thereof, one side of the bracket 4 facing the side cover 3 forms a first mounting surface, the middle of the bracket 4 is provided with an opening, the opening extends from the first mounting surface and penetrates through the whole thickness of the bracket 4, the edge of the sulfone polymer microporous liquid stopping film 2 is hermetically fixed on the first mounting surface, the second outer surface of the sulfone polymer microporous liquid stopping film 2 is arranged facing the side cover 3, and a liquid inlet cavity is formed by the side cover 3 and the side wall of the shell 1; the first outer surface of the sulfone polymer microporous liquid stopping film 2, the opening of the bracket 4 and the side wall of the shell 1 form a liquid outlet cavity; the inner wall of the liquid outlet cavity is provided with a support rib 5, the first outer surface of the sulfone polymer microporous liquid stopping film 2 and the support rib 5 are arranged at intervals, and the support rib 5 can prevent the sulfone polymer microporous liquid stopping film 2 from deforming; the supporting ribs 5 are provided with a plurality of concave parts 51 at the side facing the sulfone polymer microporous liquid stopping film 2, the concave parts 51 can be arranged at intervals, the concave parts 51 can increase the space of the liquid outlet cavity of the liquid stopping device, the liquid medicine in the liquid outlet cavity can flow out conveniently, and the flow rate of the liquid medicine is accelerated.
Or, the liquid stopper can be formed by at least two sulfone polymer micropore liquid stopping films 2, the sulfone polymer micropore liquid stopping films 2 are vertically arranged in the shell 1 at intervals, the shell 1 is sequentially divided into a first liquid inlet cavity, a liquid outlet cavity and a second liquid inlet cavity, liquid medicine can enter the first liquid inlet cavity and/or the second liquid inlet cavity simultaneously, the flux of the liquid stopper is increased, the arrangement of the sulfone polymer micropore liquid stopping films 2 further improves the filtering precision of the liquid stopper, and the liquid stopper has higher applicability.
The sulfone polymer micropore liquid stopping film 2 is arranged in the liquid stopping device, the wetting speed of the sulfone polymer micropore liquid stopping film 2 is high, when the liquid stopping device is used, liquid medicine can be filled in the liquid stopping device quickly, gas in a membrane or in the liquid stopping device in front of the membrane can be prevented from entering a human body in the infusion process, harm is caused to human health, such as air embolism and the like, meanwhile, the patient panic is avoided, and the psychological pressure of the patient can be relieved; secondly, because the liquid stopping device can be filled with liquid medicine fast, it can be understood that the existence of the liquid stopping device can not influence the flow rate of the liquid medicine, and the patient can adjust and change the flow rate of the liquid medicine at any time according to the self condition, thereby reducing the time delay when the flow rate of the liquid medicine changes and having higher applicability.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (14)

1. A sulfone polymer microporous liquid stopper membrane comprising a first porous surface, a second porous surface, and a porous body located between the first porous surface and the second porous surface, the porous body having non-directional tortuous pathways therein, wherein the sulfone polymer microporous liquid stopper membrane is for stopping an injection liquid containing a botanical extract;
in the sulfone polymer microporous liquid stopping film, the ratio of the number of holes with the aperture not more than 2.5 mu m measured by a PMI aperture tester to the whole number of the holes is less than 10 percent;
the porosity of the sulfone polymer microporous liquid stopper film is at least 60%;
the water BP value of the sulfone polymer microporous liquid stopping film is 20-50KPa, and the liquid stopping height is at least 1 m.
2. The sulfone polymer microporous liquid stopper of claim 1, wherein the number of pores having a pore diameter of more than 6 μm measured by PMI pore diameter tester is 1 to 12% of the total number of pores.
3. The sulfone polymer microporous liquid stopper of claim 1, wherein the first porous surface is defined by a plurality of first pores having an average pore size of 4 to 20 μ ι η;
the second porous surface is provided with a plurality of second holes, and the average pore diameter of the second holes is 7-28 mu m.
4. The microporous liquid stopper of claim 1, wherein the second porous surface has a pore density of second pores with a pore size of 10-35 μ ι η of 15-70 pores/40000 μ ι η2
And the ratio of the number of second holes with the aperture of 10-35 μm to the total number of second holes is not less than 70%;
on the first porous surface, the first pores with the pore diameter of 5-25 μm have a pore density of 6-50 pores/40000 μm2
5. The sulfone polymer microporous liquid stopper of claim 1, wherein the porous body comprises two side regions and a middle region, the middle region is a liquid stopper layer, one side region of the porous body near the second porous surface is a pre-filter layer, one side region of the porous body near the first porous surface is a support layer, and the liquid stopper layer has a smaller average pore size than the pre-filter layer and the support layer; the thickness of the pre-filtering layer is at least larger than 15um, and the average pore size of the pre-filtering layer is 3-25 um.
6. The sulfone polymer microporous liquid stopper of claim 1, wherein the sulfone polymer microporous liquid stopper has a thickness of 50 to 150 μ ι η and a PMI mean pore diameter of 3 to 5 μ ι η; the porosity is 70-98%.
7. The sulfone polymer microporous liquid stopper of claim 5, wherein the liquid stopper layer is a symmetrical structure having substantially the same pore size on the side of the liquid stopper layer adjacent to the pre-filter layer as the pore size on the side of the liquid stopper layer adjacent to the support layer;
the average pore diameter of the liquid stopping layer is 1-13um, and the thickness of the liquid stopping layer is 10-40 um; the average pore diameter of the supporting layer is 2-18um, and the thickness is 20-60 um.
8. The sulfone polymer microporous liquid stopper of claim 1, wherein the sulfone polymer microporous liquid stopper has a surface energy of 80-120 mN/m; the initial contact angle of the saturated saline drop to the sulfone polymer microporous liquid stop film is 55-75 degrees, and the time for the contact angle to be changed into 0 degree is 2-10 s; the work of adhesion was 100J/m2-170J/m2
9. The sulfone polymer microporous liquid stopper of claim 1, wherein the sulfone polymer microporous liquid stopper has an IPA complete bubble point of 9 to 16KPa, an IPA initial bubble point of 6 to 10 KPa; the ratio of the initial bubble point of the IPA to the complete bubble point of the IPA is (0.55-0.85): 1.
10. the sulfone polymer microporous liquid stopper of claim 5, wherein the average fiber diameter forming a porous structure within the support layer is greater than the average fiber diameter forming a porous structure within the liquid stopper layer and the pre-filter layer; the average fiber diameters of porous structures formed in the pre-filtering layer, the liquid stopping layer and the supporting layer are 1-10 microns, 0.8-7 microns and 2-12 microns in sequence; the fibers in the porous body are all in a strip-shaped structure.
11. The microporous sulfone liquid stopper of claim 1, wherein the microporous sulfone liquid stopper has a tensile strength of 3 to 10MPa, an elongation at break of 30 to 60%, and a water flux of 150--1*cm-2The interception efficiency of the sulfone polymer microporous liquid stopping film to impurity particles with the particle size not less than 5 mu m is more than 90%.
12. The method for preparing a microporous liquid stopper film of a sulfone polymer according to any one of claims 1 to 11, comprising the steps of:
s1: preparing a casting solution, and casting the casting solution on a carrier to form a liquid film; the casting solution comprises the following substances in parts by weight: 5-20 parts of sulfone polymer, 40-75 parts of first organic solvent and 6-25 parts of hydrophilic additive;
s2: placing the liquid film in air environment with temperature of 10-40 deg.C, and adjusting the absolute humidity to 15g H2O/kg-35g H2Blowing O/kg air flow onto the surface of the liquid film to pre-phase the liquid film, wherein the relative speed between the air flow and the liquid film is 0.4-0.8m/s, and the duration is 8-25 s;
s3: immersing the liquid film after the pre-phase separation into a coagulating bath for re-phase solidification to form a raw film, wherein the temperature of the coagulating bath is 10-40 ℃, and the re-phase solidification time is 30-150 s; the coagulating bath is a mixture of a second organic solvent and water; wherein the second organic solvent can be mutually soluble with water and the first organic solvent, and the volume of the second organic solvent is 5-25% of the volume of the mixture
S4; and (3) stretching the raw membrane by 1.05-1.5 times of area, cleaning in pure water, and finally drying to prepare the sulfone polymer microporous liquid stopping membrane.
13. The method for preparing a sulfone polymer microporous liquid stopper film according to claim 12, wherein the sulfone polymer comprises at least one of polyethersulfone, polysulfone and polyarylsulfone;
the hydrophilic additive comprises one or a combination of polyvinyl alcohol, polyethylene glycol, polyethyleneimine and polyvinylpyrrolidone;
the first organic solvent is at least one of dimethyl sulfoxide, dimethylformamide, caprolactam, N-ethyl pyrrolidone, dimethylacetamide and N-methyl pyrrolidone;
the second organic solvent is at least one of dimethyl sulfoxide, caprolactam, N-methyl pyrrolidone, N-ethyl pyrrolidone, dimethylformamide, dimethylacetamide, trimethyl phosphate, triethyl phosphate and r-butyrolactone.
14. The use of the sulfone polymer microporous liquid stopper according to any of claims 1 to 11, wherein the liquid stopper comprises a housing, the sulfone polymer microporous liquid stopper disposed in the housing, and a side cover sealed to the housing, the housing is provided with a drug inlet and a drug outlet in a vertical direction, the sulfone polymer microporous liquid stopper is disposed in the housing and divides the housing into a liquid inlet chamber and a liquid outlet chamber, the drug inlet is communicated with the liquid inlet chamber, and the drug outlet is communicated with the liquid outlet chamber; the liquid medicine enters the liquid inlet cavity from the medicine inlet, sequentially flows to the liquid outlet cavity through the second porous surface and the first porous surface of the sulfone polymer microporous liquid stopping film, and flows out from the medicine outlet.
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