CN111715080A - Preparation method of biodegradable high-molecular ultrafiltration membrane - Google Patents
Preparation method of biodegradable high-molecular ultrafiltration membrane Download PDFInfo
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Abstract
The invention relates to the technical field of functional polymer membrane materials, in particular to a preparation method of a biodegradable polymer ultrafiltration membrane. The invention has simple process, the raw materials are all natural polymer substances and have complete biodegradation characteristics in nature, the final product polymer ultrafiltration membrane has excellent mechanical strength, chemical stability, super-hydrophilic characteristics, pollution resistance and bacteriostasis, the retention rate of the ultrafiltration membrane is not obviously changed within 30 times of cyclic application, the service life of the ultrafiltration membrane is indirectly prolonged, and the cost is reduced.
Description
Technical Field
The invention relates to the technical field of functional polymer membrane materials, in particular to a preparation method of a biodegradable polymer ultrafiltration membrane.
Background
The functional polymer membrane is a membrane type material with selective permeability, and is also a polymer material with special mass transfer function, and is generally called as a functional membrane. The functional film generally refers to a film having a specific function (or functions) which is not possessed by general-purpose films and satisfying application specific requirements, such as an antistatic film, a heat-shrinkable film, an easy-open film, and the like. Because the functional film has different special functions, the functional film can better meet the requirement of protecting commodities or the requirement of using convenience, has better using effect and is often an indispensable material in some specific packaging fields. Functional films generally have a high technical content, good economic benefits and strong market competitiveness, and are therefore of great interest.
The ultrafiltration membrane belongs to one of functional polymer films, and an Ultrafiltration (UF) technology is a membrane separation technology between microfiltration and nanofiltration, has an average pore diameter of 3-100 nm, and has the functions of purifying, separating, concentrating a solution and the like. The interception mechanism mainly comprises the sieving effect and the electrostatic effect of the membrane, the filtering medium is an ultrafiltration membrane, and only low molecular weight solute and water can pass through the ultrafiltration membrane under the driving of pressure difference at two sides, so that the purposes of purification, separation and concentration are achieved. The ultrafiltration membrane technology has wide application range, the ultrafiltration membrane used at first is a natural animal organ membrane, the initial ultrafiltration is always used as an experimental work and is not developed, and the ultrafiltration technology does not enter the rapid development stage of industrial application until the 70 s of the 20 th century. Currently (2018), ultrafiltration membrane materials have expanded from Cellulose Acetate (CA) to Polystyrene (PS), polyvinylidene fluoride (PVDF), Polycarbonate (PC), Polyacrylonitrile (PAN), polyethersulfone PES), and nylon (PA), etc., with molecular weight cutoffs developing from 103 to 106. Because the ultrafiltration has the characteristics of simple equipment, small occupied area, unchanged phase state, low operating pressure, low material requirement, simple equipment and the like, the application range of the ultrafiltration can be rapidly extended from the research field to the practical application field, such as electronics, medicines, electrophoretic paint, beverages, food chemical industry, medical treatment, wastewater treatment and recycling and the like.
The prior art has Chinese patent with an authorization publication number of CN102580581B, and discloses a composite ultrafiltration membrane and a preparation method thereof, wherein natural cellulose and starch are subjected to acetylation reaction to prepare cellulose acetate and starch acetate, and then acetone is used as a solvent, and an initiator, a plasticizer and a hydrophilic modifier are added to prepare an ultrafiltration membrane casting solution; then preparing the polysulfone porous support membrane by a phase inversion method, directly immersing the support membrane into an ultrafiltration membrane casting solution, taking out the support membrane for natural evaporation, and forming a composite ultrafiltration structure of an internal porous support layer and a surface double-layer ultrafiltration layer after solidification through secondary thermodynamic treatment. The composite ultrafiltration membrane prepared by the method has better mechanical property and chemical stability, can be partially biodegraded, reduces the influence of the composite ultrafiltration membrane on the environment, and realizes reasonable and effective utilization of natural cellulose and starch. However, firstly, the composite ultrafiltration membrane can only be partially degraded, the degradation speed is slow, the undegraded part still causes pollution to the environment, and secondly, the hydrophilicity, the antibacterial activity and the repeated application property of the composite ultrafiltration membrane are not good enough.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a biodegradable polymeric ultrafiltration membrane, wherein the method is simple in process, raw materials are all natural polymeric substances, the biodegradable polymeric ultrafiltration membrane has complete biodegradation characteristics in nature, the final product polymeric ultrafiltration membrane has excellent mechanical strength, chemical stability, super-hydrophilic characteristics, anti-pollution capability and antibacterial effect, the retention rate of the final product polymeric ultrafiltration membrane is not significantly changed within 30 times of cyclic application, the service life of the final product polymeric ultrafiltration membrane is indirectly prolonged, and the cost is reduced.
In order to achieve the above object, the present invention provides several aspects of technical solutions as follows.
In a first aspect, a method for preparing a biodegradable polymeric ultrafiltration membrane comprises
-preparing thiolated cellulose by thiolation of cellulose powder with sodium periodate and cysteine;
-modifying starch with low molecular weight hyaluronic acid to prepare hyaluronic acid modified starch;
dissolving thiolated cellulose, hyaluronic acid modified starch and VC polyphosphate in acetone to prepare a membrane casting solution;
immersing the fiber support membrane with aminated surface into the membrane casting solution, and sequentially carrying out dimethyl sulfoxide solidification solution solidification and hot methanol solution treatment to obtain the biodegradable high-molecular ultrafiltration membrane.
The biodegradable high-molecular ultrafiltration membrane prepared by the method has complete biodegradability, the retention period in the nature is obviously reduced, the ultrafiltration membrane material has excellent mechanical strength, chemical stability, super-hydrophilic property and pollution resistance, the retention rate of the ultrafiltration membrane material is not obviously changed within 30 times of cyclic application, the service life of the ultrafiltration membrane material is indirectly prolonged, the cost is reduced, and the application field of the ultrafiltration membrane material is expanded.
Further, the preparation method of the biodegradable high-molecular ultrafiltration membrane specifically comprises the following steps:
1) preparation of thiolated cellulose:
mixing cellulose powder and sodium periodate in an aqueous solution according to a mass ratio of 1.8-2.5: 1, stirring and dispersing for at least 5 hours, adding sufficient ethylene glycol, continuously stirring and dispersing for at least 2 hours, centrifuging, taking out a product, washing with water, adding cysteine with the weight 1.4-2.0 times that of the cellulose powder into the product under the protection of nitrogen, stirring and reacting for at least 6 hours at the temperature of 37-40 ℃, centrifuging, taking out the product, washing with water, and freeze-drying; fine cellulose powder is used as a raw material, and the cellulose powder is subjected to sulfhydrylation modification by means of sodium periodate oxidation and cysteine grafting, so that cellulose macromolecules are subjected to carboxyl and sulfhydryl grafting, the activity of the cellulose macromolecules is increased, and the specific surface area of the cellulose macromolecules is increased;
2) preparing hyaluronic acid modified starch:
weighing 100 parts by weight of corn starch and a certain amount of hyaluronic acid, and placing in sufficient distilled waterAdding 8.2-9.0 parts by weight of sodium sulfate, adjusting the pH of the system to 10.5, keeping the pH, and dropwise adding 1.0-1.2 parts by volume of cross-linking agent POCl in a decrement manner under stirring3Reacting for at least 1h at the temperature of 30-32 ℃; after the reaction is finished, regulating the pH value to 5.0 by using 1mol/L hydrochloric acid, centrifuging, washing, drying and grinding, and sieving by using a sieve of at least 170 meshes; the inventor finds that after starch is modified by a certain amount of low-molecular-weight hyaluronic acid, the high-molecular ultrafiltration membrane prepared by taking the modified starch as a main component is beneficial to obviously improving the mechanical property of an ultrafiltration membrane material, and can also accelerate the biodegradation speed of the ultrafiltration membrane material, the retention period of the ultrafiltration membrane material in the nature is obviously reduced, and the method is environment-friendly;
3) preparing a casting solution:
weighing thiolated cellulose, hyaluronic acid modified starch and VC polyphosphate according to the ratio of 35-100: 100: 2.5-15.0, dissolving in sufficient acetone, adding an initiator, a plasticizer and an additive to prepare a 10-15% ultrafiltration membrane casting solution, stirring at a high speed, performing ultrasonic dispersion for at least 1h, sieving with a 140-mesh sieve, and standing for at least 24 h; the membrane casting solution is prepared by three-component structures of thiolated cellulose, hyaluronic acid modified starch and VC polyphosphate, so that the mechanical property of a final product, namely a macromolecular ultrafiltration membrane, can be remarkably enhanced, the ultrafiltration membrane material has excellent hydrophilic property, the anti-pollution capacity of the ultrafiltration membrane material is improved, the macromolecular ultrafiltration membrane material can be endowed with excellent stability, the retention rate of the macromolecular ultrafiltration membrane material is not remarkably changed within 30 times of cyclic application, and the service life of the macromolecular ultrafiltration membrane material is indirectly prolonged;
4) preparing a biodegradable high-molecular ultrafiltration membrane:
immersing the surface aminated fiber support membrane into the membrane casting solution obtained in the step 3) for 3-5 s, taking out, naturally evaporating, immersing into 18% dimethyl sulfoxide solidification solution at 55-60 ℃, taking out after solidification for at least 5h, sequentially cleaning with 5% sulfuric acid solution and distilled water, finally immersing into 15% methanol solution at 40-45 ℃, taking out after immersion for at least 6h, repeatedly cleaning with distilled water, and airing to obtain the surface aminated fiber support membrane; in the solidification process, the surface layer of the high-molecular ultrafiltration membrane can form a uniform microporous structure, and the pore diameter of the formed microporous structure can be reduced through hot methanol treatment, so that the high-molecular ultrafiltration membrane has a good pore hierarchical structure, the water flux and the average pore diameter of the high-molecular ultrafiltration membrane are reduced, and the retention rate is improved.
Further, in the step 1) of preparing the biodegradable polymeric ultrafiltration membrane, the particle size of the cellulose powder is not higher than 90 μm.
Further, in the step 1) of preparing the biodegradable high-molecular ultrafiltration membrane, the stirring speed of mixing, stirring and dispersing is 120-180 r/min.
Further, in the step 1) of preparing the biodegradable polymeric ultrafiltration membrane, the addition amount of the ethylene glycol is at least 6 times of the weight of the sodium periodate.
Further, in the step 1) of preparing the biodegradable polymeric ultrafiltration membrane, the stirring rate of the stirring reaction is at least 300 r/min.
Further, in the step 1) of preparing the biodegradable polymeric ultrafiltration membrane, the cysteine is d-cysteine. The inventor finds that the pure D-cysteine is used as a modifier to carry out sulfhydrylation modification on cellulose, so that sulfhydrylation grafting is facilitated, the final product macromolecule ultrafiltration membrane can be endowed with an excellent antibacterial effect, the antibacterial rate on staphylococcus aureus and escherichia coli can reach more than 70%, the inhibition effect on mould can also reach more than 65%, the ultrafiltration effect of the ultrafiltration membrane is remarkably improved, and the method has a positive effect on the application in the fields of drinking water purification, medicine separation and the like.
Further, in the step 2) of preparing the biodegradable polymeric ultrafiltration membrane, the weight average molecular weight of hyaluronic acid is not higher than 15000, preferably not higher than 10000.
Further, in the step 2) of preparing the biodegradable polymeric ultrafiltration membrane, the addition amount of the hyaluronic acid is 35-50 parts by weight.
Further, in the step 2) of preparing the biodegradable polymeric ultrafiltration membrane, the pH of the system is adjusted by using a saturated sodium hydroxide solution.
Further, in the step 2) of preparing the biodegradable high-molecular ultrafiltration membrane, the cross-linking agent POCl is dropwise added in a reducing way3The method comprises the following steps:
dripping 40-50% of the total amount within 1 min;
after 3-5 min, dripping 30-35% of the total amount within 1 min;
after 3-5 min, dripping 20-25% of the total amount within 1 min;
after 3-5 min, dripping 10-15% of the total amount within 1 min. The inventors have surprisingly found that when the cross-linking agent POCl is added in a gradually decreasing dropwise manner as described herein3The hyaluronic acid modified starch is prepared by dropwise adding the hyaluronic acid modified starch into a mixed solution of corn starch and sodium sulfate and crosslinking the hyaluronic acid modified starch, and the hyaluronic acid modified starch, thiolated cellulose and VC polyphosphate are combined to form a three-component structure to prepare a membrane casting solution, so that the tensile strength of a final product, namely a high-molecular ultrafiltration membrane material, can be increased to over 30MPa, the high-molecular ultrafiltration membrane material can obtain the super-hydrophilic characteristic that the water contact angle is not higher than 5 degrees, the anti-pollution capacity of the ultrafiltration membrane material is remarkably improved, and the service life of the ultrafiltration membrane material is further prolonged.
Further, in the step 3) of preparing the biodegradable polymeric ultrafiltration membrane, the initiator is dibutyltin dilaurate, and the addition amount of the initiator is 0.12-0.18% of the total mass of the ultrafiltration membrane casting solution.
Further, in the step 3) of preparing the biodegradable polymeric ultrafiltration membrane, the VC polyphosphate can be prepared by the existing methods, including but not limited to the method comprising the following steps:
1) preparing VC aqueous solution, adjusting the pH value of the VC aqueous solution to 10.5 by using calcium hydroxide solution, and reacting for at least 1h at 40-42 ℃;
2) adding calcium chloride accounting for 4.8-5.0% of the weight of VC and sodium trimetaphosphate accounting for 1.05-1.20 times of the weight of VC into the solution obtained in the step 1), maintaining the pH of the solution at 10.5 by using a calcium hydroxide solution, and finishing the reaction when the content of free VC is monitored to be constant;
3) regulating the pH of the reaction liquid obtained in the step 2) to be neutral by hydrochloric acid, and directly spray-drying to obtain the catalyst.
Further, in the step 3) of preparing the biodegradable high-molecular ultrafiltration membrane, the plasticizer is tributyl citrate and polyethylene glycol in a weight ratio of 1: 3-4, and the addition amount of the plasticizer is 1.5-2.0% of the total mass of the ultrafiltration membrane casting solution.
Further, in the step 3) of preparing the biodegradable high-molecular ultrafiltration membrane, the additive is polyvinylpyrrolidone, and the addition amount of the additive is 0.3-1.5% of the total mass of the ultrafiltration membrane casting solution.
Further, in the step 3) of preparing the biodegradable high-molecular ultrafiltration membrane, the stirring speed of ultra-high-speed stirring is not lower than 8000r/min and is at least 1 h.
Further, in the step 3) of preparing the biodegradable high-molecular ultrafiltration membrane, the ultrasonic frequency of ultrasonic dispersion is 50-80 KHz, and the ultrasonic intensity is 0.4-0.8 w/cm2。
Further, in the step 4) of preparing the biodegradable polymeric ultrafiltration membrane, the surface-aminated fiber support membrane can be subjected to surface modification treatment by co-deposition of polydopamine and polyethyleneimine, so that the surface of the fiber support membrane is provided with amino groups.
Further, in the step 4) of preparing the biodegradable high-molecular ultrafiltration membrane, the natural evaporation time is not less than 5 min.
The method has simple process, prepares the membrane casting solution by utilizing three component structures of thiolated cellulose, hyaluronic acid modified starch and VC polyphosphate, and then coagulates the membrane casting solution on the surface layer of a fiber support membrane to prepare the macromolecular ultrafiltration membrane material. According to the application, the biodegradable high-molecular ultrafiltration membrane is prepared by solidifying the membrane casting solution with three component structures of thiolated cellulose, hyaluronic acid modified starch and VC polyphosphate to the fiber support membrane with aminated surface, amino on the surface of the fiber support membrane can be subjected to cross-linking reaction with sulfhydryl groups and carboxyl groups in the thiolated cellulose, the hyaluronic acid modified starch, so that the final ultrafiltration membrane has excellent mechanical strength, chemical stability, super-hydrophilic property, anti-pollution capability and antibacterial effect, the interception rate of the ultrafiltration membrane is not remarkably changed within 30 times of cyclic application, the service life of the ultrafiltration membrane is indirectly prolonged, and the ultrafiltration membrane can be widely applied to the technical fields of drinking water purification, sewage and wastewater treatment, extraction and purification of effective substances, drug separation and the like.
In a second aspect, a biodegradable polymeric ultrafiltration membrane is prepared by the preparation method of the first aspect.
The invention has the beneficial effects that:
1) under a specific plasticizer system, preparing a membrane casting solution by utilizing three component structures of thiolated cellulose, hyaluronic acid modified starch and VC polyphosphate, and then solidifying the membrane casting solution on the surface layer of a fiber support membrane to prepare a high-molecular ultrafiltration membrane material;
2) after a certain amount of low-molecular-weight hyaluronic acid is used for modifying starch, the modified starch is used as a main component to prepare the high-molecular ultrafiltration membrane, so that the mechanical property of an ultrafiltration membrane material is obviously improved, the biodegradation speed of the ultrafiltration membrane material can be accelerated, the retention period of the ultrafiltration membrane material in the natural world is obviously reduced, and the method is environment-friendly;
3) the tensile strength of the final product, namely the polymer ultrafiltration membrane material, is improved to more than 30MPa, and the polymer ultrafiltration membrane material can obtain the super-hydrophilic characteristic that the water contact angle is not higher than 5 degrees, so that the pollution resistance of the ultrafiltration membrane material is obviously improved, the polymer ultrafiltration membrane material also has excellent stability, the retention rate of the polymer ultrafiltration membrane material is not obviously changed within 30 times of cyclic application, and the service life of the polymer ultrafiltration membrane material is indirectly prolonged;
4) the high molecular ultrafiltration membrane has excellent antibacterial effect, the antibacterial rate of the high molecular ultrafiltration membrane on staphylococcus aureus and escherichia coli can reach more than 70%, the high molecular ultrafiltration membrane can also play an inhibiting role on mould of more than 65%, the ultrafiltration effect of the ultrafiltration membrane is remarkably improved, and the high molecular ultrafiltration membrane has positive effects on the application in the fields of drinking water purification, medicine separation and the like.
The invention adopts the technical scheme for achieving the purpose, makes up the defects of the prior art, and has reasonable design and convenient operation.
Drawings
The foregoing and/or other objects, features, advantages and embodiments of the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic diagram of a process for preparing a thiolated cellulose of the present invention;
FIG. 2 is a diagram showing the statistics of retention rate of the polymeric ultrafiltration membrane material of the present invention after multiple applications;
FIG. 3 is a statistical schematic diagram of water contact angles of the polymeric ultrafiltration membrane material of the present invention after multiple applications.
Detailed Description
Those skilled in the art can appropriately substitute and/or modify the process parameters to implement the present disclosure, but it is specifically noted that all similar substitutes and/or modifications will be apparent to those skilled in the art and are deemed to be included in the present invention. While the products and methods of making described herein have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the products and methods of making described herein may be made and utilized without departing from the spirit and scope of the invention.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated by reference herein in their entirety. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, multiples, etc. are by weight unless otherwise indicated; additional instructions include, but are not limited to, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5(1 to 5)" is described, the described range is understood to include ranges of "1 to 4(1 to 4)", "1 to 3(1 to 3)", "1 to 2(1 to 2) and 4 to 5(4 to 5)", "1 to 3(1 to 3) and 5", and the like. Where numerical ranges are described herein, unless otherwise stated, the ranges are intended to include the endpoints of the ranges, and all integers and fractions within the ranges.
When the term "about" is used to describe a numerical value or an end point value of a range, the disclosure should be understood to include the specific value or end point referred to.
Furthermore, "or" means "or" unless expressly indicated to the contrary, rather than "or" exclusively. For example, condition a "or" B "applies to any of the following conditions: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to mean no limitation on the number of occurrences (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of an element or component also include the plural unless the singular is explicitly stated.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation. The use of the phrase "comprising one of the elements does not exclude the presence of other like elements in the process, method, article, or apparatus that comprises the element.
The materials, methods, and examples described herein are illustrative only and not intended to be limiting unless otherwise specified. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
The present invention is described in detail below.
Example 1: a biodegradable high molecular ultrafiltration membrane:
this example provides a biodegradable polymeric ultrafiltration membrane, which is prepared by the following steps:
1) preparation of thiolated cellulose:
mixing 90-micron cellulose powder and sodium periodate in an aqueous solution according to a mass ratio of 2:1, stirring and dispersing for 5 hours at a speed of 150r/min, adding glycol with the weight being 10 times that of the sodium periodate, continuously stirring and dispersing for 2 hours, centrifuging, taking out a product, washing with water, adding D-cysteine with the weight being 1.6 times that of the cellulose powder into the product under the protection of nitrogen, stirring and reacting for 6 hours at a temperature of 38 ℃ at a speed of 600r/min, centrifuging, taking out the product, washing with water, and freeze-drying;
2) preparing hyaluronic acid modified starch:
weighing 100g of corn starch and 40g of hyaluronic acid with weight-average molecular weight of 8000, putting the corn starch and the hyaluronic acid into sufficient distilled water, adding 9g of sodium sulfate, adjusting the pH of a system to 10.5 by using saturated sodium hydroxide solution, keeping the pH, and dropwise adding 1mL of cross-linking agent POCl into the system in a decrement manner under stirring3Reacting for 2 hours at the temperature of 31 ℃; after the reaction is finished, regulating the pH value to 5.0 by using 1mol/L hydrochloric acid, centrifuging, washing, drying and grinding, and sieving by using a 170-mesh sieve;
3) preparing a casting solution:
weighing 45g of thiolated cellulose, 100g of hyaluronic acid modified starch and 10gVC g of polyphosphate, dissolving in 1354g of acetone, adding 2.325g of dibutyltin dilaurate, 4.65g of tributyl citrate, 18.6g of polyethylene glycol and 15.5g of polyvinylpyrrolidone, preparing into an ultrafiltration membrane casting solution, stirring at a super speed of 10000r/min for 1h, and then stirring at a super speed of 60KHz and 0.5w/cm for 1h2Carrying out ultrasonic dispersion for 1h under the condition, sieving by a 140-mesh sieve, and standing for 36 h;
4) preparing a biodegradable high-molecular ultrafiltration membrane:
and (3) immersing the fiber support membrane with the aminated surface into the membrane casting solution obtained in the step 3) for 5s, taking out, naturally evaporating for 5min, immersing into 18% dimethyl sulfoxide solidification solution at the temperature of 58 ℃, taking out after solidification for 5h, sequentially cleaning by using 5% sulfuric acid solution and distilled water, finally immersing into 15% methanol solution at the temperature of 42 ℃, taking out after immersion for 6h, repeatedly cleaning by using distilled water, and airing to obtain the fiber support membrane.
Additionally, the step of preparing the biodegradable polymeric ultrafiltration membrane according to this embodiment further includes the following limitations a to C:
A. in the step 2), the cross-linking agent POCl is dripped in a decrement way3The method comprises the following steps:
40 percent of the total amount, namely 0.4mL is dripped in 1min,
after 5min, 30 percent of the total amount, namely 0.3mL is dripped in the mixture within 1min,
after 5min, dripping 20 percent of the total amount, namely 0.2mL, within 1min,
after 5min, dripping 10 percent of the total amount within 1min, namely 0.1 mL;
B. in the step 3), the VC polyphosphate ester is prepared by the following method: preparing VC aqueous solution, adjusting the pH value to 10.5 by using calcium hydroxide solution, and reacting for 2 hours at 40 ℃; adding calcium chloride with the weight of 5.0% of VC and sodium trimetaphosphate with the weight of 1.1 times of VC, maintaining the pH of the solution at 10.5 by using a calcium hydroxide solution, finishing the reaction when the content of free VC is monitored to be unchanged, adjusting the pH of the reaction solution to be neutral by using hydrochloric acid, and directly spray-drying to obtain the finished product.
C. In the step 4), the surface aminated fiber support membrane can be subjected to surface modification treatment through co-deposition of polydopamine and polyethyleneimine, so that the surface of the fiber support membrane is provided with amino groups.
Example 2: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that no thiolated cellulose was added to the casting solution of this example, and the deficit was made up with hyaluronic acid modified starch.
Example 3: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that VC polyphosphate was not added to the casting solution of this example, and the deficiency was made up by hyaluronic acid modified starch.
Example 4: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that the cellulose in this example was not modified.
Example 5: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that the cysteine that was used to modify the cellulose powder in this example was all L-cysteine.
Example 6: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that the cysteine that was used to modify the cellulose powder in this example was all racemic cysteine.
Example 7: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that the corn starch in this example was unmodified.
Example 8: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that the weight average molecular weight of hyaluronic acid when corn starch was modified in this example was 5000.
Example 9: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that the weight average molecular weight of hyaluronic acid in the modification of corn starch in this example is 20000.
Example 10: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that in this example, the hyaluronic acid was replaced with sodium alginate having a weight average molecular weight of 20000 when corn starch was modified.
Example 11: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that in this example, the crosslinking agent POCl was added dropwise during the corn starch modification3The method comprises the following steps:
dripping 25 percent of the total amount within 1min, namely 0.25mL,
after 5min, 25 percent of the total amount, namely 0.25mL is dripped in the mixture within 1min,
after 5min, 25 percent of the total amount, namely 0.25mL is dripped in the mixture within 1min,
after 5min, 25% of the total amount, i.e. 0.25mL, was added dropwise over 1 min.
Example 12: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that in this example, the crosslinking agent POCl was added dropwise during the corn starch modification3The method comprises the following steps:
dropping 10 percent of the total amount within 1min, namely 0.1mL,
after 5min, dripping 20 percent of the total amount, namely 0.2mL, within 1min,
after 5min, 30 percent of the total amount, namely 0.3mL is dripped in the mixture within 1min,
after 5min, 40% of the total amount, i.e. 0.4mL, was added dropwise over 1 min.
Example 13: another biodegradable high molecular ultrafiltration membrane:
this example provides another biodegradable polymeric ultrafiltration membrane material prepared according to substantially the same formulation and method as in example 1, except that in this example, the crosslinking agent POCl was added dropwise during the corn starch modification3The method comprises the following steps: 100 percent of the total amount is dripped within 1min, namely, the dripping is finished at one time.
Experimental example 1: detecting the ultrafiltration performance of the macromolecular ultrafiltration membrane:
the biodegradable polymeric ultrafiltration membranes in examples 1 to 13 were tested according to HY/T050-1999 hollow fiber ultrafiltration membrane test method, and the performance indexes are shown in Table 1.
TABLE 1 biodegradable Polymer Ultrafiltration Membrane Performance
| Examples | Water flux/L (m)2·h)-1 | Retention rate/%) | Porosity/% | Tensile strength/ |
| 1 | 62.8 | 99.6 | 62.5 | 30.5 |
| 2 | 60.2 | 94.3 | 60.2 | 22.8 |
| 3 | 58.3 | 98.2 | 60.1 | 30.3 |
| 4 | 63.5 | 94.4 | 59.6 | 24.4 |
| 5 | 60.1 | 99.5 | 60.5 | 28.6 |
| 6 | 61.5 | 99.0 | 63.2 | 28.0 |
| 7 | 58.2 | 95.1 | 60.4 | 22.1 |
| 8 | 62.1 | 99.3 | 61.4 | 31.2 |
| 9 | 55.6 | 94.1 | 60.8 | 20.4 |
| 10 | 57.7 | 96.6 | 61.1 | 22.8 |
| 11 | 54.6 | 94.6 | 59.8 | 24.6 |
| 12 | 55.1 | 97.4 | 60.2 | 28.3 |
| 13 | 58.2 | 96.8 | 60.3 | 25.5 |
As can be seen from table 1, the polymeric ultrafiltration membranes in preferred embodiments 1 and 8 of the present application have relatively excellent water flux, rejection rate and porosity, and at the same time, the tensile strength thereof can reach more than 30MPa, and analysis shows that unmodified cellulose or unmodified cellulose has an influence on the mechanical strength of the ultrafiltration membrane, and incomplete modification of corn starch can also cause a great reduction in the rejection effect and the mechanical strength of the polymeric ultrafiltration membrane.
Experimental example 2: and (3) degradation detection:
the degradation of each of the biodegradable polymeric ultrafiltration membranes of examples 1 to 13 was measured according to the following methods:
1. soaking a macromolecular ultrafiltration membrane in 1mol/L sulfuric acid solution to determine the acid degradation effect;
2. the natural degradation of the macromolecular ultrafiltration membrane is determined according to JISK6950-94 Standard test method for biodegradable plastics, and the time required for complete degradation is calculated by inverse method, for example, if 30 days of degradation is 50% (by weight), the time required for complete degradation is 60 days. The statistical results are shown in table 2.
TABLE 2 degradation
As can be seen from table 2, preferred examples 1 and 8 of the present application have very excellent degradation effect, and can be completely degraded within 30d of the soil, and it can be seen that the degradation rate of the prepared polymeric ultrafiltration membrane is significantly reduced without modifying starch as described in the present application, so that it takes longer time to completely degrade.
Experimental example 3: and (3) cyclic application detection:
the retention rates of the solutes 1, 10, 20 and 30 times were measured and retained according to the method described in experimental example 1, and the surface water contact angles of the retained solutes 1, 10, 20 and 30 times were measured after the polymeric ultrafiltration membrane was dried, respectively, and the statistical results are shown in fig. 2 and fig. 3, respectively. As can be seen from fig. 2, the polymeric ultrafiltration membrane material has excellent stability, the retention rate of the polymeric ultrafiltration membrane material has no significant change within 30 times of cyclic application, the service life of the polymeric ultrafiltration membrane material is indirectly prolonged, and the use cost is reduced, as can be seen from fig. 3, the polymeric ultrafiltration membranes in preferred embodiments 1 and 8 of the present application can maintain excellent superhydrophilic characteristics within 20 times, and the characteristics can significantly improve the anti-pollution capability of the ultrafiltration membrane material.
Experimental example 4: and (3) detection of bacteriostatic action:
respectively infiltrating the ultrafiltration membranes in the examples 1-13 with staphylococcus aureus, escherichia coli and mould suspension ultra-dilute suspension, counting the total amount of microorganisms adhered to the ultrafiltration membranes, standing for 48 hours at room temperature, then counting the total amount of microorganisms of the same batch of ultrafiltration membranes in the same group, and calculating the relative bacteriostasis rate, wherein the counting result is shown in table 3.
TABLE 3 bacteriostatic action
| Examples | Staphylococcus aureus inhibition/%) | Inhibition of E.coli/%) | Inhibition of mold/%) |
| 1 | 73.8 | 75.4 | 70.2 |
| 2 | 16.2 | 28.8 | 15.5 |
| 3 | 70.5 | 71.3 | 66.0 |
| 4 | 22.6 | 35.2 | 20.3 |
| 5 | 40.0 | 45.1 | 31.8 |
| 6 | 38.3 | 39.6 | 27.9 |
| 7 | 67.1 | 70.8 | 60.5 |
| 8 | 71.6 | 72.2 | 68.0 |
| 9 | 72.2 | 73.5 | 65.1 |
| 10 | 69.8 | 70.9 | 63.3 |
| 11 | 72.4 | 75.3 | 60.9 |
| 12 | 71.3 | 70.4 | 65.4 |
| 13 | 70.1 | 72.2 | 63.6 |
As can be seen from table 3, most of the polymeric ultrafiltration membrane materials in embodiments 1 to 13 of the present application all have a certain inhibitory effect on staphylococcus aureus, escherichia coli and mold fungi, and it can be seen that, in particular, when thiolated cellulose is not added, cellulose is not modified, cellulose is modified by pure l-cysteine, and modification of cellulose by racemic cysteine has a large effect on the bacteriostatic effect of the polymeric ultrafiltration membrane materials, so that the bacteriostatic effect is significantly reduced, which is not favorable for applications in the fields of special occasions, long-term use and food products.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. Therefore, the contents of the verification of the respective examples are not described herein, and the excellent points of the present invention will be described only by representative examples 1 to 13 and experimental examples 1 to 4.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.
Claims (10)
1. A preparation method of a biodegradable high-molecular ultrafiltration membrane is characterized by comprising the following steps:
-preparing thiolated cellulose by thiolation of cellulose powder with sodium periodate and cysteine;
-modifying starch with low molecular weight hyaluronic acid to prepare hyaluronic acid modified starch;
dissolving thiolated cellulose, hyaluronic acid modified starch and VC polyphosphate in acetone to prepare a membrane casting solution;
immersing the fiber support membrane with aminated surface into the membrane casting solution, and sequentially carrying out dimethyl sulfoxide solidification solution solidification and hot methanol solution treatment to obtain the biodegradable high-molecular ultrafiltration membrane.
2. The method of claim 1, wherein: the method comprises the following steps:
1) preparation of thiolated cellulose:
mixing cellulose powder and sodium periodate in an aqueous solution according to a mass ratio of 1.8-2.5: 1, stirring and dispersing for at least 5 hours, adding sufficient ethylene glycol, continuously stirring and dispersing for at least 2 hours, centrifuging, taking out a product, washing with water, adding cysteine with the weight 1.4-2.0 times that of the cellulose powder into the product under the protection of nitrogen, stirring and reacting for at least 6 hours at the temperature of 37-40 ℃, centrifuging, taking out the product, washing with water, and freeze-drying;
2) preparing hyaluronic acid modified starch:
weighing 100 parts by weight of corn starch and a certain amount of hyaluronic acid, putting the corn starch and the hyaluronic acid into sufficient distilled water, adding 8.2-9.0 parts by weight of sodium sulfate, adjusting the pH value of the system to 10.5, keeping the pH value, and dropwise adding 1.0-1.2 parts by volume of cross-linking agent while stirringPOCl3Reacting for at least 1h at the temperature of 30-32 ℃; after the reaction is finished, regulating the pH value to 5.0 by using 1mol/L hydrochloric acid, centrifuging, washing, drying and grinding, and sieving by using a sieve of at least 170 meshes;
3) preparing a casting solution:
weighing thiolated cellulose, hyaluronic acid modified starch and VC polyphosphate according to the ratio of 35-100: 100: 2.5-15.0, dissolving in sufficient acetone, adding an initiator, a plasticizer and an additive to prepare 10-15% of an ultrafiltration membrane casting solution, stirring at a high speed, performing ultrasonic dispersion for at least 1h, sieving with a 140-mesh sieve, and standing for at least 24 h;
4) preparing a biodegradable high-molecular ultrafiltration membrane:
and (3) immersing the fiber support membrane with the aminated surface into the membrane casting solution obtained in the step 3) for 3-5 s, taking out, naturally evaporating, immersing into 18% dimethyl sulfoxide solidification solution at 55-60 ℃, taking out after solidification for at least 5h, sequentially cleaning with 5% sulfuric acid solution and distilled water, finally immersing into 15% methanol solution at 40-45 ℃, taking out after immersion for at least 6h, repeatedly cleaning with distilled water, and airing to obtain the fiber support membrane.
3. The method according to claim 1 or 2, characterized in that: the particle diameter of the cellulose powder is not more than 90 μm.
4. The method according to any one of claims 1 to 3, wherein: the cysteine is a dextro-cysteine.
5. The method according to any one of claims 1 to 4, wherein: the weight average molecular weight of the hyaluronic acid is not higher than 15000, preferably not higher than 10000.
6. The method according to any one of claims 2 to 5, wherein: the dropping crosslinking agent POCl3The mode of (1) is dropping in a reduced amount.
7. The method according to any one of claims 2 to 6, wherein: the dropping crosslinking agent POCl3The method specifically comprises the following steps:
dripping 40-50% of the total amount within 1 min;
after 3-5 min, dripping 30-35% of the total amount within 1 min;
after 3-5 min, dripping 20-25% of the total amount within 1 min;
after 3-5 min, dripping 10-15% of the total amount within 1 min.
8. The method according to any one of claims 2 to 7, wherein: the plasticizer is tributyl citrate and polyethylene glycol in a weight ratio of 1: 3-4, and the addition amount of the plasticizer is 1.5-2.0% of the total mass of the ultrafiltration membrane casting solution.
9. The method according to any one of claims 1 to 8, wherein: the VC polyphosphate ester is prepared by a method comprising the following steps:
1) preparing VC aqueous solution, adjusting the pH value of the VC aqueous solution to 10.5 by using calcium hydroxide solution, and reacting for at least 1h at 40-42 ℃;
2) adding calcium chloride accounting for 4.8-5.0% of the weight of VC and sodium trimetaphosphate accounting for 1.05-1.20 times of the weight of VC into the solution obtained in the step 1), maintaining the pH of the solution at 10.5 by using a calcium hydroxide solution, and finishing the reaction when the content of free VC is monitored to be constant;
3) regulating the pH of the reaction liquid obtained in the step 2) to be neutral by hydrochloric acid, and directly spray-drying to obtain the catalyst.
10. A biodegradable polymeric ultrafiltration membrane obtainable by the method of any one of claims 1 to 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980303A (en) * | 2021-12-07 | 2022-01-28 | 北京大学深圳研究院 | Hyaluronic acid and biodegradable high-molecular modified material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238056A (en) * | 1961-03-27 | 1966-03-01 | Pall Corp | Microporous materials and process of making the same |
| CN102580581A (en) * | 2012-03-07 | 2012-07-18 | 华南理工大学 | Composite ultrafiltration film and preparation method thereof |
| CN103041448A (en) * | 2013-01-17 | 2013-04-17 | 苏州博创同康生物工程有限公司 | Compound polysaccharide hemostatic material and preparation method and application thereof |
| CN103724641A (en) * | 2013-11-30 | 2014-04-16 | 青岛海之林生物科技开发有限公司 | Preparation method for blend membrane of sodium alginate, amylum and carboxymethyl cellulose |
| CN106823861A (en) * | 2017-02-09 | 2017-06-13 | 浙江大学 | A kind of hollow fiber compound nanofiltration membrane based on natural polymer and preparation method thereof |
| CN106947025A (en) * | 2017-04-27 | 2017-07-14 | 安庆师范大学 | A kind of preparation method based on starch graft acrylic acid and the compound water-keeping gel of sodium alginate, slag |
| CN107325192A (en) * | 2017-06-30 | 2017-11-07 | 武汉理工大学 | A kind of sulfhydrylation Cellulose nanocrystal and preparation method thereof |
-
2020
- 2020-05-20 CN CN202010431496.3A patent/CN111715080A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238056A (en) * | 1961-03-27 | 1966-03-01 | Pall Corp | Microporous materials and process of making the same |
| CN102580581A (en) * | 2012-03-07 | 2012-07-18 | 华南理工大学 | Composite ultrafiltration film and preparation method thereof |
| CN103041448A (en) * | 2013-01-17 | 2013-04-17 | 苏州博创同康生物工程有限公司 | Compound polysaccharide hemostatic material and preparation method and application thereof |
| CN103724641A (en) * | 2013-11-30 | 2014-04-16 | 青岛海之林生物科技开发有限公司 | Preparation method for blend membrane of sodium alginate, amylum and carboxymethyl cellulose |
| CN106823861A (en) * | 2017-02-09 | 2017-06-13 | 浙江大学 | A kind of hollow fiber compound nanofiltration membrane based on natural polymer and preparation method thereof |
| CN106947025A (en) * | 2017-04-27 | 2017-07-14 | 安庆师范大学 | A kind of preparation method based on starch graft acrylic acid and the compound water-keeping gel of sodium alginate, slag |
| CN107325192A (en) * | 2017-06-30 | 2017-11-07 | 武汉理工大学 | A kind of sulfhydrylation Cellulose nanocrystal and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980303A (en) * | 2021-12-07 | 2022-01-28 | 北京大学深圳研究院 | Hyaluronic acid and biodegradable high-molecular modified material and preparation method thereof |
| CN113980303B (en) * | 2021-12-07 | 2023-09-15 | 北京大学深圳研究院 | Hyaluronic acid and biodegradable polymer modified material and preparation method thereof |
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