CN111495219B - Preparation method of ethylene/vinyl alcohol copolymer film for blood purification - Google Patents

Preparation method of ethylene/vinyl alcohol copolymer film for blood purification Download PDF

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CN111495219B
CN111495219B CN202010242023.9A CN202010242023A CN111495219B CN 111495219 B CN111495219 B CN 111495219B CN 202010242023 A CN202010242023 A CN 202010242023A CN 111495219 B CN111495219 B CN 111495219B
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何春菊
王建秀
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Donghua University
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Abstract

The present invention relates to a method for preparing a blood-purifying ethylene/vinyl alcohol copolymer membrane using NIPS or TIPS. The method comprises the following steps: mixing propyl betaine, EVOH, a catalyst and an organic solvent, reacting, precipitating, cleaning, drying, then homogenizing and mixing with EVOH and the organic solvent, defoaming and forming a film to obtain the catalyst. The method is simple, rapid and low in cost, and the obtained copolymer membrane has good biological pollution resistance.

Description

Preparation method of ethylene/vinyl alcohol copolymer film for blood purification
Technical Field
The invention belongs to the field of preparation of functional polymer membrane materials, and particularly relates to a method for preparing an ethylene/vinyl alcohol copolymer membrane for blood purification by using non-solvent induced phase separation (NIPS) or Thermally Induced Phase Separation (TIPS).
Background
With the increasing demand for biological materials and artificial organs, membrane materials for blood purification are receiving more and more attention. The blood purification is to take the blood of a patient out of the body, remove certain pathogenic substances (toxins) in the blood through a purification device, or supplement nutrient components into the blood, so as to achieve the purposes of purifying the blood and treating diseases. The treatment modes mainly comprise hemodialysis, hemofiltration, plasma separation, membrane abdominal dialysis and the like. Wherein, the purifying membrane is the most important part in the purifying equipment, and the blood purifying treatment effect is determined by the quality of the purifying membrane material.
Currently, blood purification membranes are prepared clinically using polymers such as cellulose and its derivatives, Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), Polysulfone (PSF), polyether sulfone (PES), and ethylene/vinyl alcohol copolymer (EVOH) by suitable processing types such as thermal phase separation, non-solvent phase separation, or melt-drawing (Journal of Membrane Science, 2002, 210, 411-. However, these membrane materials all face the problem of membrane bio-contamination, mainly because the proteins in plasma can be rapidly adsorbed and deposited on the membrane surface in a short time to form a protein adsorption layer, thereby causing the membrane pores to be blocked, and affecting the purification effect and efficiency (Biomaterials,2008,29, 4285-. To address such problems, patients often require the use of drugs to inhibit the formation of biological contaminants on the membrane surface. The anticoagulant heparin is most typical of these, but the use of heparin causes spontaneous bleeding in some patients. Therefore, development of a blood purification membrane material having high efficiency against biological contamination is a trend in the future.
Membrane modification with anti-biofouling media such as polyethylene glycol and its derivatives, zwitterions, and polyvinylpyrrolidone are the predominant strategies for improving the anti-fouling performance of membranes. Wherein the zwitterionic polymer is a novel material with no pollution and strong biocompatibility. It binds strongly to water molecules through electrostatic interactions, and the hydrated layer formed provides a physical and energy barrier to reduce the interaction of contaminants with the material surface. Currently, surface coating, surface grafting, and blend modification have been used to introduce zwitterions into the membrane matrix. The surface coating is simple and convenient, but the obtained coating layer is often only temporary and cannot be used for multiple times. The surface grafting method can solve the problem of instability of the coating, and a grafting chain can form a stable covalent bond with the surface of the membrane. However, surface grafting requires cumbersome steps and harsh conditions, and furthermore, the graft chains may block the pores of the membrane and reduce the permeability of the membrane. Blending modification is therefore the most effective way to increase the membrane material's resistance to biological contamination. However, the solubility of zwitterions in organic solvents is limited due to hydration of multi-site positive and negative ion groups, so that the application of the zwitterions in blending modification is caused.
In recent years, amphiphilic zwitterionic polymers have received much attention as blending modifiers. Because the hydrophobic chain segments in the polymer form strong hydrophobic interaction with the membrane matrix, the solubility of zwitterions in organic solvents is improved, and the blending compatibility of the zwitterions and the membrane matrix can be maintained. In addition, the ethylene/vinyl alcohol copolymer (EVOH) with excellent mechanical strength, thermal stability, chemical reagent resistance and biological non-toxicity contains active functional group hydroxyl (-OH), and the amphiphilic zwitterionic membrane prepared by modifying the EVOH has higher application potential in the field of blood purification. (Carbohydrate polymers,2017,165:266-
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing an ethylene/vinyl alcohol copolymer membrane for blood purification by NIPS or TIPS, so as to overcome the defects of poor solubility of an amphiphilic zwitterionic polymer in an organic solvent, poor biological pollution resistance of the membrane and the like in the membrane material in the prior art.
The invention provides an ethylene/vinyl alcohol copolymer film, which is obtained by grafting ethyl betaine to ethylene/vinyl alcohol copolymer EVOH, then homogenizing and mixing the EVOH with an organic solvent, defoaming and forming the film.
The propyl betaine is NCO-propyl betaine.
The present invention also provides a method for preparing an ethylene/vinyl alcohol copolymer film using a NIPS or TIPS, comprising:
(1) mixing propyl betaine, EVOH, a catalyst and an organic solvent, reacting, precipitating, cleaning and drying to obtain the amphiphilic zwitterionic polymer, wherein the mass ratio of the amphiphilic zwitterionic polymer to EVOH is (0.1-7): (3-9), the catalyst and the organic solvent respectively account for 0.01-1% and 70-95% of the total mass of the reaction system;
(2) and (2) homogenizing and mixing the EVOH, the amphiphilic zwitterionic polymer and the organic solvent in the step (1), defoaming, and forming a film by using a non-solvent induced phase separation NIPS or thermally induced phase separation TIPS (dissolved phase separation) film casting solution to obtain the ethylene/vinyl alcohol copolymer film, wherein the mass ratio of the EVOH, the amphiphilic zwitterionic polymer and the organic solvent is (6-16): (2-10): (74-92).
And (2) in the step (1), the propyl betaine is NCO-propyl betaine.
The preparation method of the NCO-propyl betaine comprises the following steps: diisocyanate, dimethyl amine substances and a quaternizing agent are mixed according to the mass ratio of (1-6): (1-4): (1-5) reacting at 20-90 ℃ for 0.5-48h, and drying to obtain the product.
The diisocyanate comprises one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate.
The dimethyl amine substance comprises 3- (dimethylamino) -1-propylamine or N, N-dimethylethanolamine.
The quaternizing agent comprises one of 1, 3-propane sultone, 3-bromopropionic acid and beta-propane lactone.
The catalyst in the step (1) is an amine catalyst or an organic metal compound.
The organometallic compound includes dibutyltin dilaurate.
The amine catalyst comprises triethylamine, pentamethyl diethylenetriamine, N-ethyl morpholine, bis-dimethylaminoethyl ether or N, N-dimethyl cyclohexylamine.
The organic solvent in the step (1) is any one or a mixture of any two of high-boiling point strong-polarity aprotic solvents.
The organic solvent in the step (1) comprises at least one of dimethyl sulfoxide, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformamide.
The reaction temperature in the step (1) is 20-100 ℃, and the reaction time is 0.5-24 h.
The precipitating agent precipitated in the step (1) is any one of polar solvents or a mixture of any two of polar solvents.
The organic solvent in the step (2) is any one or a mixture of any two of a high-boiling point strong-polarity aprotic solvent and a high-boiling point alcohol solvent.
The organic solvent in the step (2) comprises at least one of dimethyl sulfoxide, 1, 3-propylene glycol, sulfolane, glycerol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, diethylene glycol and triethylene glycol.
The homogenizing and mixing temperature in the step (2) is 25-180 ℃, and the homogenizing and mixing time is 0.5-36 h; the defoaming time is 0.5-36 h.
The film forming mode in the step (2) comprises flat scraping film or spinning hollow fiber film by a spinning machine.
The flat-plate film scraping method comprises the following steps: scraping the casting solution to form a film, pre-evaporating for 0-10min, and then soaking the film into a coagulating bath at 10-80 ℃ for curing to form the film.
The method for spinning the hollow fiber membrane by the spinning machine comprises the following steps: and (3) filter-pressing the membrane casting solution and the core solution, then extruding the nascent fiber through two concentric hollow fiber spinneret orifices, allowing the nascent fiber to pass through a distance of 0-50cm in air, then entering a coagulating bath at 10-80 ℃ for forming, and then drawing and winding to obtain the composite fiber.
The coagulating bath and the core liquid are both composed of organic solvent and water, and the mass fraction of the organic solvent is 0-85%.
The invention also provides an application of the ethylene/vinyl alcohol copolymer film in blood purification.
The ethylene/vinyl alcohol copolymer film can remove pathogenic substances in blood.
The invention takes ethylene/vinyl alcohol copolymer as a basic component, takes ethylene/vinyl alcohol copolymer grafted NCO sulfobetaine as a modified component, and prepares the ethylene/vinyl alcohol copolymer film with biological pollution resistance by a blending modification method.
Aiming at the defects of the prior art, the invention develops a simple, convenient, economic and effective method for grafting the propyl betaine coupled with isocyanate to the ethylene/vinyl alcohol copolymer through covalent bonds, and the hydrophobic chains in the prepared amphiphilic zwitterionic polymer and the ethylene/vinyl alcohol copolymer matrix form strong hydrophobic-hydrophobic interaction, which is beneficial to the dissolution of the zwitterionic polymer and simultaneously avoids the elution of zwitterions in the membrane preparation process, so that the obtained membrane has lasting and stable biological pollution resistance, the performance of the membrane in blood purification is improved, and the risk of complications of patients in the blood purification process is reduced.
The ethylene/vinyl alcohol copolymer membrane prepared by the invention has simple process and low preparation cost, and the pure water flux recovery rate of the membrane are far superior to those of the ethylene/vinyl alcohol copolymer which is not modified by zwitterions. In addition, the biological pollution resistance of the membrane prepared by the method is greatly improved.
Advantageous effects
(1) The amphiphilic zwitterion prepared by the method has good compatibility with an ethylene/vinyl alcohol copolymer base material and good solubility in an organic solvent;
(2) the modified ethylene/vinyl alcohol copolymer casting solution prepared by the invention has good film forming property, and the surfaces of the prepared flat membrane and the hollow fiber membrane are smooth;
(3) the average pore size of the amphoteric ionized ethylene/vinyl alcohol copolymer membrane prepared by the invention is 6.0nm-294.2 nm; when the protein pollution resistance test is carried out, the flux recovery rate is increased to 70-93%; the protein adsorption capacity is reduced to 4.5-10.9 mug/cm2(ii) a The hemolysis rate is reduced to 0.8-2.3%.
Drawings
FIG. 1 is a chart of the infrared spectrum of NCO-sulfopropylbetaine in example 1.
FIG. 2 is a nuclear magnetic hydrogen spectrum of NCO-sulfopropyl betaine in example 1.
FIG. 3 is an infrared image of the unmodified ethylene/vinyl alcohol copolymer film and the zwitterionic modified ethylene/vinyl alcohol copolymer film of example 1.
FIG. 4 is a surface SEM photograph of a zwitterionic modified ethylene/vinyl alcohol copolymer film of example 1.
FIG. 5 is a scheme showing the synthesis scheme of Zwitterionic Cellulose Acetate (ZCA) in comparative example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The examples relate to the main reagent specifications and sources as shown in table 1.
TABLE 1 Main materials, specifications and sources
Name (R) Specification of Company(s)
EVOH E105B Nippon Coli Kabushiki Kaisha
Catalysts AR Aladdin reagent
Organic solvents AR SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Diisocyanates AR Aladdin reagent
Dimethyl amines AR Anyingji chemical
Quaternary ammonium agents AR Anyingji chemical
BSA AR SINOPHARM CHEMICAL REAGENT Co.,Ltd.
(1) Membrane pore size testing
The porosity and average pore size of the membrane were determined by dry-wet weighing. The film samples were immersed in deionized water at 25 ℃ for 24 hours and weighed after excess water was wiped off with filter paper. The wet film sample was then dried in vacuo to constant weight. Porosity (. epsilon.) and average pore diameter (r) of the membranem) Calculated by the Guerout-Elford-Ferry equation:
Figure BDA0002432865510000041
Figure BDA0002432865510000051
wherein WwAnd Wd(g) Weight of dry and wet films, respectively, pw(g·cm-3) Is the density of water, A (cm)2) Is the area of the membrane, δ (cm) is the thickness of the membrane, η (8.9X 10)-4Pas) is the viscosity of water, Q (m)3·s-1) Is the volume of water permeated, and Δ P (0.1MPa) is the transmembrane pressure difference.
(2) Flux testing
Loading the flat membrane or the hollow fiber membrane into a closed filtering device, conveying a supply liquid to the upper surface of the flat membrane or the inner surface of the hollow fiber membrane of the membrane component through a peristaltic pump, and collecting a filtered liquid obtained by filtering through a measuring cylinder. During testing, firstly, pre-pressing for 30min by using deionized water under the transmembrane pressure difference of 0.15MPa, then reducing the pressure to 0.1MPa, recording the permeable volume within a certain time, testing once every 5 minutes, and then replacing the plasma in the container with 1.0 g.L-1After the flux of the BSA solution is stabilized, the flux value is recorded, and each sample is tested for 5 times to obtain an average value. The flux calculation equation is as follows:
Figure BDA0002432865510000052
wherein J is the flux (L.m)-2·h-1) V is permeate volume (L), Δ t is time tested (h), A is effective membrane area (m)2)(AFlat sheet membrane＝3.95×10-3m2，AHollow fiber membrane＝1.88×10-3m2)。
The dynamic filtration pollution test quantitatively characterizes the pollution condition of the ultrafiltration membrane by alternately filtering pure water and a pollutant system and comparing the change condition of water flux. The specific process is as follows: first, pure water is filtered to obtain a stable water flux Jw1Then replacing the feed liquid with a pollutant feed liquid BSA solution to obtain stable flux, then taking the membrane out of the testing device, washing the membrane with pure water for 30 minutes, then carrying out a water flux test, replacing the feed liquid with the pure water, and measuring the water flux Jw2And the circulation can be carried out for a plurality of times according to the experimental requirements.
The Flux Recovery Rate (FRR) parameter of the membrane against protein contamination is calculated as follows:
Figure BDA0002432865510000053
(3) protein adsorption
Use of Micro BCATMProtein assay kits detect quantitative adsorption of BSA. The area is 1cm2The membrane of (a) was incubated in phosphate buffer solution (PBS, pH 8.5) overnight, followed by 1mg · ml at 37 ℃-1Soaking in BSA solution for 12 h. The sample was gently washed 3 times with PBS and then immersed in 2ml of a 2 wt% aqueous solution of Sodium Dodecyl Sulfate (SDS) at 37 ℃ for 1h to separate the adsorbed protein. Finally, 20 μ L of the wash solution was transformed into a 96-well plate, and 200 μ L of BCA working solution was added to the wash solution. The protein concentration was determined by measuring the absorbance at 562 nm.
(4) Rate of hemolysis
Fresh rabbit blood was centrifuged at 1500r.p.m for 10min to obtain a red blood cell suspension. The area is 1cm2The membrane was washed 3 times with physiological saline, and then 2ml of physiological saline was added to soak in a 24-well plate at 37 ℃ for 2 hours. Then 30 μ L of red blood cell suspension (C ═ C) was added at 37 ℃10g/L) was added to each well for 1 h. 2ml of diluted blood in each well was transferred to an EP tube and centrifuged at 2500 r.p.m. for 5 minutes. After that, 20 μ L of the supernatant was transferred to a 96-well plate. Percent hemolysis was calculated by measuring absorbance at 545nm using a microplate reader. The Hemolysis Rate (HR) was calculated as follows:
Figure BDA0002432865510000061
wherein A isSIs the absorption value of the sample, ANIs the absorption value of a negative control (0.9 wt% physiological saline), APIs the absorbance of the positive control (ultrapure water).
In the following examples, the percentages and parts of the components referred to are, unless otherwise specified, percentages by mass and parts by mass.
Example 1
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-sulfopropyl betaine
27 parts of isophorone diisocyanate (27g), 12 parts of 3- (dimethylamino) -1-propylamine, 17 parts of 1, 3-propanesultone were reacted at 20 ℃ for 48 hours, and the precipitate was dried.
(2) NCO-sulfopropyl betaine grafted ethylene/vinyl alcohol copolymer
50 parts of ethylene/vinyl alcohol copolymer, 20 parts of NCO-sulfopropyl betaine and 0.4 part of dibutyltin dilaurate are dissolved in 350 parts of dimethyl sulfoxide, and after reaction at 50 ℃ for 8 hours, the solution is precipitated in deionized water, washed and dried.
The second step is that: preparing a casting solution: putting 52 parts of ethylene/vinyl alcohol copolymer, 20 parts of ethylene/vinyl alcohol copolymer grafted NCO sulfobetaine and 328 parts of dimethyl sulfoxide into a reaction vessel, stirring at the temperature of 80 ℃ for 10 hours, standing and defoaming for 12 hours to obtain a clear and transparent casting solution.
The third step: preparing a hollow fiber membrane by an NIPS method: and (2) performing filter pressing on 350 parts of the casting membrane stock solution and 350 parts of 50% dimethyl sulfoxide water core solution, allowing nascent fibers extruded by a hollow fiber spinneret plate with the diameter of 800 mu m to pass through a distance of 25cm in air, then allowing the nascent fibers to enter 300 parts of deionized water at the temperature of 20 ℃ for forming, and performing drafting and winding to finally obtain the hollow fiber membrane.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 17.1nm, and the water flux can reach 301 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 81%, and the amount of protein adsorbed on the membrane surface was 7.7. mu.g/cm2The hemolysis rate was 1.9%.
ATR-FTIR on the surface of the unmodified ethylene/vinyl alcohol copolymer film and the modified ethylene/vinyl alcohol copolymer film is shown in FIG. 3, 1562cm-1Peak of N-H bending vibration and 1194cm-1Of (C) is-SO3The stretching vibration peak of the group proves that NCO-sulfopropyl betaine is successfully grafted to the ethylene/vinyl alcohol copolymer. The surface appearance of the zwitterionic modified ethylene/vinyl alcohol copolymer membrane is shown in figure 4, the pores on the surface of the membrane are uniformly distributed, and the pore size is about 30 nm.
Example 2
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-carboxypropylbetaine
30 parts of dicyclohexylmethane diisocyanate (30g), 20 parts of 3- (dimethylamino) -1-propylamine and 25 parts of 1, 3-propanesultone were reacted at 90 ℃ for 0.5h, and the precipitate was dried.
(2) NCO-carboxypropylbetaine grafted ethylene/vinyl alcohol copolymers
18 parts of ethylene/vinyl alcohol copolymer, 14 parts of NCO-sulfopropyl betaine and 0.003 part of dibutyltin dilaurate are dissolved in 608 parts of N, N-dimethylacetamide, reacted at 20 ℃ for 24 hours, and then the solution is precipitated in deionized water, washed and dried.
The second step is that: preparing a casting solution: putting 58 parts of ethylene/vinyl alcohol copolymer, 36 parts of ethylene/vinyl alcohol copolymer grafted NCO carboxyl betaine, 72 parts of 1, 3-propylene glycol and 195 parts of sulfolane into a reaction vessel, stirring at the temperature of 180 ℃ for 0.5h, standing and defoaming for 0.5h to obtain clear and transparent casting solution.
The third step: preparing a hollow fiber membrane by a TIPS method: and (2) performing filter pressing on 350 parts of casting film stock solution and 350 parts of 85% sulfolane water core solution, allowing nascent fibers extruded by a hollow fiber spinneret plate with the diameter of 800 mu m to pass through a distance of 50cm in air, then allowing the nascent fibers to enter 300 parts of deionized water at 80 ℃ for forming, and performing drafting and winding to finally obtain the hollow fiber membrane.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 6.0nm, and the water flux can reach 128 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 85%, and the amount of protein adsorbed on the membrane surface was 7.1. mu.g/cm2The hemolysis rate was 1.7%.
Example 3
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-sulfopropyl betaine
2 parts of dicyclohexylmethane diisocyanate (2g), 2 parts of 3- (dimethylamino) -1-propylamine and 2 parts of 1, 3-propanesultone were reacted at 50 ℃ for 12 hours, and the precipitate was dried.
(2) NCO-sulfopropyl betaine grafted ethylene/vinyl alcohol copolymer
Dissolving 2 parts of ethylene/vinyl alcohol copolymer, 2 parts of NCO-sulfopropyl betaine and 0.04 part of triethylamine in 9.3 parts of N-methylpyrrolidone, reacting at 100 ℃ for 0.5h, precipitating the solution in acetone, cleaning and drying.
The second step is that: preparing a casting solution: placing 6 parts of ethylene/vinyl alcohol copolymer, 2 parts of ethylene/vinyl alcohol copolymer grafted NCO sulfobetaine and 92 parts of N-methyl pyrrolidone into a reaction vessel, standing and defoaming for 36 hours at the temperature of 25 ℃, and obtaining a clear and transparent casting solution.
The third step: preparing a flat membrane by an NIPS method: and pouring 90 parts of the casting solution on a glass plate, scraping the casting solution into a film by using a 200-micrometer scraper, pre-evaporating the film for 1min, and then soaking the film into 200 parts of deionized water at 20 ℃ to cure the film.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 294.2nm, and the water flux can reach 1540 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 80%, and the protein adsorption amount on the membrane surface was 8.2. mu.g/cm2Rate of hemolysisThe content was 1.4%.
Example 4
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-sulfopropyl betaine
30 parts of hexamethylene diisocyanate (30g) and 15 parts of 3- (dimethylamino) -1-propylamine were reacted at 50 ℃ for 2 hours, then 18 parts of 1, 3-propanesultone were added to continue the reaction for 16 hours, and the precipitate was dried.
(2) NCO-sulfopropyl betaine grafted ethylene/vinyl alcohol copolymer
40 parts of ethylene/vinyl alcohol copolymer, 20 parts of NCO-sulfopropyl betaine and 0.3 part of triethylamine are dissolved in 200 parts of N, N-dimethylformamide and 200 parts of N-methylpyrrolidone, and after reaction for 8 hours at 50 ℃, the solution is precipitated in tetrahydrofuran, washed and dried.
The second step is that: preparing a casting solution: putting 48 parts of ethylene/vinyl alcohol copolymer, 24 parts of ethylene/vinyl alcohol copolymer grafted NCO sulfobetaine, 164 parts of N, N-dimethylformamide and 164 parts of N-methylpyrrolidone into a reaction vessel, carrying out ultrasonic treatment at the temperature of 80 ℃ for 1 hour, and standing and defoaming for 12 hours to obtain a clear and transparent casting solution.
The third step: preparing a hollow fiber membrane by an NIPS method: and (2) filter-pressing 350 parts of the casting membrane stock solution and 350 parts of pure water core solution, then directly feeding nascent fiber extruded by a hollow fiber spinneret plate with the diameter of 800 mu m into 300 parts of 30% N, N-dimethylformyl aqueous solution at 10 ℃ for forming, and then drawing and winding to finally obtain the hollow fiber membrane.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 30.5nm, and the water flux can reach 332 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 81%, and the amount of protein adsorbed on the membrane surface was 7.9. mu.g/cm2The hemolysis rate was 1.8%.
Example 5
(1) Synthesis of NCO-carboxypropylbetaine
3 parts of dicyclohexylmethane diisocyanate (3g) and 1.2 parts of N, N-dimethylethanolamine are reacted at 20 ℃ for 12h, 2 parts of 3-bromopropionic acid are subsequently added and the reaction is continued for 36h, and the precipitate is dried.
(2) NCO-carboxypropylbetaine grafted ethylene/vinyl alcohol copolymers
Dissolving 4 parts of ethylene/vinyl alcohol copolymer, 2 parts of NCO-sulfopropyl betaine and 0.06 part of pentamethyldiethylenetriamine in 10 parts of N, N-dimethylacetamide and 10 parts of N, N-dimethylacetamide, reacting at 50 ℃ for 8 hours, precipitating the solution in methanol, cleaning and drying.
The second step is that: preparing a casting solution: placing 8 parts of ethylene/vinyl alcohol copolymer, 8 parts of ethylene/vinyl alcohol copolymer grafted NCO carboxyl betaine, 30 parts of 1, 3-propylene glycol and 54 parts of glycerol into a reaction vessel, stirring at the temperature of 150 ℃ for 10 hours, standing and defoaming for 4 hours to obtain clear and transparent casting solution.
The third step: preparing a flat membrane by a TIPS method: and pouring 90 parts of the casting solution on a glass plate, scraping the casting solution into a film by using a 200-micrometer scraper, immediately immersing the film into 200 parts of 50% 1, 3-propanediol aqueous solution at 80 ℃ to solidify and form the film.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 70.9nm, and the water flux can reach 529 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 85%, and the amount of protein adsorbed on the membrane surface was 6.7. mu.g/cm2The hemolysis rate was 1.4%.
Example 6
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-carboxypropylbetaine
25 parts of toluene diisocyanate (25g), 15 parts of 3- (dimethylamino) -1-propylamine were reacted at 20 ℃ for 12 hours, then 10 parts of β -propiolactone was added further for a further reaction for 36 hours, and the product was dried under vacuum for 24 hours.
(2) NCO-carboxypropylbetaine grafted ethylene/vinyl alcohol copolymers
60 parts of ethylene/vinyl alcohol copolymer, 2 parts of NCO-sulfopropyl betaine and 0.5 part of N-ethyl morpholine are dissolved in 400 parts of N-methyl pyrrolidone and 400 parts of dimethyl sulfoxide, and after reaction for 2 hours at 100 ℃, the solution is precipitated in isopropanol, washed and dried.
The second step is that: preparing a casting solution: placing 40 parts of ethylene/vinyl alcohol copolymer, 20 parts of ethylene/vinyl alcohol copolymer grafted NCO carboxyl betaine and 410 parts of triethylene glycol into a reaction vessel, stirring at the temperature of 180 ℃ for 6 hours, standing and defoaming for 16 hours to obtain the casting solution.
The third step: preparing a hollow fiber membrane by a TIPS method: and (2) performing filter pressing on 350 parts of casting membrane stock solution and 350 parts of core solution containing 50% of triethylene glycol aqueous solution, then extruding nascent fibers through a hollow fiber spinneret plate with the diameter of 800 mu m in air for 50cm, then putting the nascent fibers into 10% N-methylpyrrolidine aqueous solution with the temperature of 40 ℃ for forming, and finally obtaining the hollow fiber membrane through drafting and winding.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 142.6nm, and the water flux can reach 732 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 70%, and the protein adsorption amount on the membrane surface was 10.9. mu.g/cm2The hemolysis rate was 1.9%.
Example 7
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-sulfopropyl betaine
20 parts of diphenylmethane diisocyanate (20g), 20 parts of N, N-dimethylethanolamine and 18 parts of 1, 3-propane sultone were reacted at 50 ℃ for 12 hours, and the precipitate was dried.
(2) NCO-sulfopropyl betaine grafted ethylene/vinyl alcohol copolymer
30 parts of ethylene/vinyl alcohol copolymer, 20 parts of NCO-sulfopropyl betaine and 0.15 part of bis-dimethylamino ethyl ether are dissolved in 200 parts of dimethyl sulfoxide, reacted for 12 hours at 50 ℃, and then precipitated, cleaned and dried in a mixed solution of deionized water and methanol.
The second step is that: preparing a casting solution: putting 49 parts of ethylene/vinyl alcohol copolymer, 35 parts of ethylene/vinyl alcohol copolymer grafted NCO sulfobetaine and 616 parts of glycerol into a reaction vessel, stirring for 4 hours at the temperature of 150 ℃, standing and defoaming for 6 hours to obtain a clear and transparent casting solution.
The third step: preparing a hollow fiber membrane by a TIPS method: and (2) performing pressure filtration on 350 parts of the membrane casting solution and 350 parts of 70% dimethyl sulfoxide water core solution, feeding nascent fibers extruded by a hollow fiber spinneret plate with the diameter of 800 mu m into 300 parts of deionized water at 30 ℃ for forming after a distance of 5cm in air, and performing drafting and winding to finally obtain the hollow fiber membrane.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 187.0nm, and the water flux can reach 941 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 90%, and the amount of protein adsorbed on the membrane surface was 5.4. mu.g/cm2The hemolysis rate was 1.0%.
Example 8
(1) Synthesis of NCO-carboxypropylbetaine
27 parts of isophorone diisocyanate (27g), 12 parts of 3- (dimethylamino) -1-propylamine, 17 parts of 3-bromopropionic acid were reacted at 50 ℃ for 12 hours, and the precipitate was dried.
(2) NCO-carboxypropylbetaine grafted ethylene/vinyl alcohol copolymers
30 parts of an ethylene/vinyl alcohol copolymer, 20 parts of NCO-sulfopropylbetaine and 0.1 part of dibutyltin dilaurate were dissolved in 150 parts of N, N-dimethylacetamide, reacted at 50 ℃ for 8 hours, and then the solution was precipitated in a mixed solution of methanol and tetrahydrofuran, washed and dried.
The second step is that: preparing a casting solution: 64 parts of ethylene/vinyl alcohol copolymer, 16 parts of ethylene/vinyl alcohol copolymer grafted NCO carboxyl betaine, 40 parts of N, N-dimethylformamide and 680 parts of N, N-dimethylacetamide are placed in a reaction vessel, stirred at the temperature of 80 ℃ for 10 hours, and kept stand for defoaming for 12 hours to obtain clear and transparent casting solution.
The third step: preparing a hollow fiber membrane by an NIPS method: and (2) carrying out filter pressing on 350 parts of the casting membrane stock solution and 350 parts of pure water core solution, then extruding the nascent fiber through a hollow fiber spinneret plate with the diameter of 800 mu m, carrying out a distance of 10cm in air, then carrying out molding in 300 parts of 50% N, N-dimethylacetamide aqueous solution at 25 ℃, and carrying out drafting and winding to finally obtain the hollow fiber membrane.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 229.2nm, and the water flux can reach 1197 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 79%, and the protein adsorption amount on the membrane surface was 8.3. mu.g/cm2The hemolysis rate was 1.7%.
Example 9
(1) Synthesis of NCO-carboxypropylbetaine
28 parts of hexamethylene diisocyanate (28g), 12 parts of 3- (dimethylamino) -1-propylamine and 17 parts of beta-propiolactone were reacted at 20 ℃ for 48 hours, and the product was vacuum-dried for 24 hours.
(2) NCO-carboxypropylbetaine grafted ethylene/vinyl alcohol copolymers
20 parts of ethylene/vinyl alcohol copolymer, 20 parts of NCO-carboxypropylbetaine and 0.4 part of dibutyltin dilaurate are dissolved in 150 parts of N, N-dimethylformamide and reacted for 8 hours at the temperature of 50 ℃, and then the solution is precipitated in deionized water, washed and dried.
The second step is that: preparing a casting solution: putting 52 parts of ethylene/vinyl alcohol copolymer, 20 parts of ethylene/vinyl alcohol copolymer grafted NCO carboxyl betaine and 328 parts of N, N-dimethylformamide into a reaction vessel, stirring at the temperature of 80 ℃ for 10 hours, standing and defoaming for 12 hours to obtain a clear and transparent solution.
The third step: preparing a hollow fiber membrane by an NIPS method: and (2) performing filter pressing on 350 parts of casting membrane stock solution and 350 parts of 85% N, N-dimethylformamide water core solution, feeding nascent fibers extruded by a hollow fiber spinneret plate with the diameter of 800 mu m into 30 ℃ and 300 parts of deionized water for forming after a distance of 25cm in air, and drafting and winding to finally obtain the hollow fiber membrane.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 27.8nm, and the water flux can reach 298 L.m-2·h-1After filtering the BSA protein solution, the pure water flux recovery was 86%, and the protein adsorption on the membrane surface was 7.0. mu.g/cm2The hemolysis rate was 1.6%.
Example 10
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-sulfopropyl betaine
27 parts of hexamethylene diisocyanate (27g), 15 parts of N, N-dimethylethanolamine and 17 parts of 1, 3-propane sultone were reacted at 90 ℃ for 0.5h, and the precipitate was dried.
(2) NCO-sulfopropyl betaine grafted ethylene/vinyl alcohol copolymer
30 parts of ethylene/vinyl alcohol copolymer, 20 parts of NCO-sulfopropyl betaine and 0.5 part of triethylamine are dissolved in 200 parts of dimethyl sulfoxide, and after the reaction is carried out for 8 hours at the temperature of 50 ℃, the solution is precipitated in ethanol, washed and dried.
The second step is that: preparing a casting solution: putting 32 parts of ethylene/vinyl alcohol copolymer, 20 parts of ethylene/vinyl alcohol copolymer grafted NCO sulfobetaine, 32 parts of N-methyl pyrrolidone and 296 parts of dimethyl sulfoxide into a reaction vessel, stirring at the temperature of 60 ℃ for 12 hours, standing and defoaming for 12 hours to obtain a clear and transparent casting solution.
The third step: preparing a hollow fiber membrane by an NIPS method: and (2) performing filter pressing on 350 parts of the casting membrane stock solution and 350 parts of 50% dimethyl sulfoxide water core solution, then feeding nascent fibers extruded by a hollow fiber spinneret plate with the diameter of 800 mu m into 30 ℃ and 300 parts of 50% dimethyl sulfoxide water solution for forming after a distance of 10cm in air, and then performing drafting and winding to finally obtain the hollow fiber membrane.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 99.8nm, and the water flux can reach 616 L.m-2·h-1After filtering the BSA protein solution, the pure water flux recovery was 84%, and the protein adsorption on the membrane surface was 7.4. mu.g/cm2The hemolysis rate was 1.7%.
Example 11
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-carboxypropylbetaine
3 parts dicyclohexylmethane diisocyanate (3g), 2 parts 3- (dimethylamino) -1-propylamine were reacted at 90 ℃ for 0.5h, then 2 parts beta-propiolactone was added further for 0.5h, and the precipitate was dried.
(2) NCO-carboxypropylbetaine grafted ethylene/vinyl alcohol copolymers
3 parts of ethylene/vinyl alcohol copolymer, 2 parts of NCO-carboxypropylbetaine and 0.04 part of dibutyltin dilaurate are dissolved in 20 parts of N-methylpyrrolidone, and after reaction for 10 hours at 50 ℃, the solution is precipitated in butanone, washed and dried.
The second step is that: preparing a casting solution: placing 12 parts of ethylene/vinyl alcohol copolymer, 5 parts of ethylene/vinyl alcohol copolymer grafted NCO carboxyl betaine and 83 parts of N-methyl pyrrolidone into a reaction vessel, stirring at the temperature of 50 ℃ for 14 hours, standing and defoaming for 8 hours to obtain a clear and transparent casting solution.
The third step: preparing a flat membrane by an NIPS method: and pouring 90 parts of the casting solution on a glass plate, scraping the casting solution into a film by using a 200-micrometer scraper, pre-evaporating the film for 2min, and then soaking the film into 200 parts of 15% N-methylpyrrolidone aqueous solution at 30 ℃ to cure the film.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 40.2nm, and the water flux can reach 403 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 84%, and the amount of protein adsorbed on the membrane surface was 7.1. mu.g/cm2The hemolysis rate was 1.5%.
Example 12
The first step is as follows: preparation of amphiphilic zwitterionic polymer:
(1) synthesis of NCO-sulfopropyl betaine
2.7 parts of isophorone diisocyanate (2.7g), 1.2 parts of 3- (dimethylamino) -1-propylamine were reacted at 20 ℃ for 24h, then 1.7 parts of 1, 3-propanesultone were added further to continue the reaction for 24h, and the precipitate was dried.
(2) NCO-sulfopropyl betaine grafted ethylene/vinyl alcohol copolymer
3.5 parts of ethylene/vinyl alcohol copolymer, 1.5 parts of NCO-sulfopropyl betaine and 0.1 part of N, N-dimethyl cyclohexylamine are dissolved in 15 parts of N, N-dimethyl acetamide, reacted for 8 hours at 50 ℃, and then the solution is precipitated in deionized water, washed and dried.
The second step is that: preparing a casting solution: placing 10 parts of ethylene/vinyl alcohol copolymer, 10 parts of ethylene/vinyl alcohol copolymer grafted NCO sulfobetaine, 20 parts of diethylene glycol and 60 parts of glycerol into a reaction vessel, stirring at the temperature of 180 ℃ for 10 hours, standing and defoaming for 0.5 hour to obtain clear and transparent casting solution.
The third step: preparing a flat membrane by a TIPS method: and pouring 90 parts of the casting solution on a glass plate, scraping the casting solution into a film by using a 200-micrometer scraper, pre-evaporating the film for 10min, and then soaking the film into 200 parts of 10% diethylene glycol aqueous solution at 10 ℃ to solidify and form the film.
The average pore size of the anti-biological pollution ethylene/vinyl alcohol copolymer membrane is 14.7nm, and the water flux can reach 244 L.m-2·h-1After filtering the BSA protein solution, the recovery rate of pure water flux was 93%, and the amount of protein adsorbed on the membrane surface was 4.5. mu.g/cm2The hemolysis rate was 0.8%.
Comparative example 1
The preparation method of ZCA comprises the following steps: as shown in FIG. 5, the preparation of zwitterionic cellulose acetate can be divided into three steps.
(1) 10.0g of cellulose acetate was placed in 200mL of DMSO containing sodium periodate (5.0g), and the pH was adjusted to 3.5 using 1M concentrated sulfuric acid. The reaction was carried out at 45 ℃ for 6h under a dark nitrogen stream. After the reaction was completed, excess periodate was reacted with ethylene glycol, and the mixture was poured into deionized water. The dialdehyde cellulose acetate obtained was filtered, washed several times with deionized water and ethanol, and dried under vacuum.
(2) The 6.0g oxidized cellulose acetate suspension was acidified in acetate buffer (300mL, pH 4.5, acetic acid/sodium acetate) and stirred for 15 minutes. After introduction of nitrogen, 3 equivalents of N, N-dimethyl-1, 3-propanediamine were added at 45 ℃ and reacted for 6 h. Subsequently, 5% (w/v) aqueous sodium borohydride (2 eq) was slowly added to the mixture for reaction for 3 h. The resulting mixture was poured into a large excess of deionized water with vigorous stirring. The cellulose acetate with the side-chain tertiary amine groups is filtered off, washed thoroughly with deionized water and ethanol and dried in vacuo.
(3) A total of 5.0g of the previously obtained product, 3.0g of sodium 2-bromoethanesulfonate (SBES) and 80mL of DMSO was mixed into the reaction system. After vigorous stirring at 60 ℃ for 24h, the resulting solution was precipitated into deionized water. The obtained zwitterionic cellulose acetate was washed with deionized water and ethanol, then, vacuum dried.
Preparation of the film: the film-forming polymer (ZCA or CA) (15wt percent), the pore-forming agent (PVP) (5wt percent) and the organic solvent (NMP) (20wt percent) are put into a reaction vessel, stirred at the temperature of 50 ℃ for 12 hours, and kept stand and defoamed for 12 hours. The casting solution was poured onto a nonwoven fabric supported by a glass plate and scraped into a film using a 200 μm doctor blade, and immediately immersed in deionized water at room temperature.
And (3) comparison:
Figure BDA0002432865510000131

Claims (8)

1. an ethylene/vinyl alcohol copolymer film is characterized in that propyl betaine is grafted with ethylene/vinyl alcohol copolymer EVOH, then the obtained amphiphilic zwitterionic polymer is mixed with EVOH and an organic solvent in a homogenizing way, and defoaming and film forming are carried out to obtain the ethylene/vinyl alcohol copolymer film; the propyl betaine is NCO-propyl betaine, and the mass ratio of the EVOH to the amphiphilic zwitterionic polymer to the organic solvent is (6-16): (2-10): (74-92).
2. A method for preparing an ethylene/vinyl alcohol copolymer film using NIPS or TIPS, comprising the steps of:
(1) mixing propyl betaine, EVOH, a catalyst and an organic solvent, reacting, precipitating, cleaning and drying to obtain the amphiphilic amphoteric ionic polymer, wherein the catalyst and the organic solvent respectively account for 0.01-1% and 70-95% of the total mass of the reaction system, the propyl betaine is NCO-propyl betaine, the catalyst is an amine catalyst or an organic metal compound, the reaction temperature is 20-100 ℃, and the reaction time is 0.5-24 hours;
(2) and (2) homogenizing and mixing the EVOH, the amphiphilic zwitterionic polymer and the organic solvent in the step (1), defoaming, and forming a film by using a non-solvent induced phase separation NIPS or thermally induced phase separation TIPS (dissolved phase separation) film casting solution to obtain the ethylene/vinyl alcohol copolymer film, wherein the mass ratio of the EVOH, the amphiphilic zwitterionic polymer and the organic solvent is (6-16): (2-10): (74-92).
3. The method according to claim 2, wherein the organic solvent in step (1) comprises at least one of dimethylsulfoxide, N-dimethylacetamide, N-methylpyrrolidone, and N, N-dimethylformamide.
4. The method as claimed in claim 2, wherein the preparation of NCO-propyl betaine comprises: diisocyanate, dimethyl amine substances and a quaternizing agent are mixed according to the mass ratio of (1-6): (1-4): (1-5) reacting at 20-90 ℃ for 0.5-48h, and drying to obtain the product.
5. The method of claim 4, wherein the diisocyanate comprises one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate; the dimethyl amine substances comprise 3- (dimethylamino) -1-propylamine or N, N-dimethylethanolamine; the quaternizing agent comprises one of 1, 3-propane sultone, 3-bromopropionic acid and beta-propane lactone.
6. The method according to claim 2, wherein the organic solvent in step (2) comprises at least one of dimethyl sulfoxide, 1, 3-propanediol, sulfolane, glycerol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, diethylene glycol and triethylene glycol.
7. The method according to claim 2, wherein the temperature of the homogeneous mixing in the step (2) is 25-180 ℃, and the time of the homogeneous mixing is 0.5-36 h; the defoaming time is 0.5-36 h; the film forming mode comprises flat scraping film or spinning hollow fiber film by a spinning machine.
8. Use of a membrane according to claim 1 for blood purification.
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