CN116041776B - Preparation method of high connectivity microporous wall air pocket bionic polyvinyl alcohol structure body containing composite layer - Google Patents
Preparation method of high connectivity microporous wall air pocket bionic polyvinyl alcohol structure body containing composite layer Download PDFInfo
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 47
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 125000003158 alcohol group Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 18
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000008234 soft water Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004891 communication Methods 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012744 reinforcing agent Substances 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 2
- 239000000416 hydrocolloid Substances 0.000 claims description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000000463 material Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 12
- 229920002472 Starch Polymers 0.000 description 11
- 235000019698 starch Nutrition 0.000 description 9
- 239000008107 starch Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000499 gel Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 239000004088 foaming agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000002101 nanobubble Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 229940100486 rice starch Drugs 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 229940100445 wheat starch Drugs 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000003928 nasal cavity Anatomy 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a preparation method of a high connectivity microporous wall cavitation bionic polyvinyl alcohol structure containing a composite layer, which is characterized in that a long main chain water-soluble crosslinkable high molecular polymer and a short chain water-soluble crosslinkable oligomer are mixed to prepare a polyvinyl alcohol mixed solution, clean gas is introduced into the polyvinyl alcohol mixed solution to prepare a finished product, and the high connectivity microporous wall cavitation bionic polyvinyl alcohol structure containing the composite layer prepared by the preparation method has the performances of cavitation and hole wall microstructure, and the drainage property, thermal structure stability and the like of the product are improved.
Description
Technical Field
The invention relates to the field of polyvinyl alcohol structures, in particular to a preparation method of a high connectivity microporous wall air pocket bionic polyvinyl alcohol structure containing a composite layer.
Background
The design and development of the medical instrument can be applied to the development of new treatment programs, solves the clinical limitations and bottlenecks which cannot be overcome by the traditional medical programs, practices the clinical requirements which cannot be met by the traditional medical instrument, and provides the body paste protection for medical care patients which cannot be achieved by the traditional medical behaviors. Along with the evolution of society and medical level, new clinical demands are also continuously put forward, and according to new clinical application demands, besides breakthrough from mechanical structure and integration with optomechanical and electrical communication, appropriate biomedical engineering materials, such as polyvinyl alcohol, polyelectrolyte, polyurethane, polylactic acid, polynorbornene, polytetrafluoroethylene, polymethacrylate, polysiloxane, silicone, natural polymer, resin and the like, are fully considered to be modified for clinical application.
Polyurethane or nonwoven materials, while achieving substantial safety in biocompatibility and providing disposal, exhibit limitations in clinical handling due to poor tissue anti-adhesion properties, which also becomes a clinical risk for medical care and wound management. Therefore, the polyvinyl alcohol can provide a very good clinical application scheme clinically due to good biocompatibility, tissue anti-tackiness, high permeability and excellent apricot mechanical property, can be used in a dry state and a wet state, has no problem of disintegration pollution, is used for solving the clinical requirement of a soft high-support drainage material, is used for preparing a polyvinyl alcohol foam innovative bionic drainage material with an air pocket and a pore wall microstructure, and is successfully developed into a high-clean production process for preparing the polyvinyl alcohol foam innovative bionic drainage material. The safety performance of the polyvinyl alcohol structure is improved.
Disclosure of Invention
Accordingly, the invention provides a preparation method of a high connectivity microporous wall air pocket bionic polyvinyl alcohol structure body containing a composite layer, which solves the problems.
The preparation method of the high connectivity microporous wall air pocket bionic polyvinyl alcohol structure body containing the composite layer comprises the following steps:
(1) Mixing a long-main-chain water-soluble crosslinkable high polymer and a short-chain water-soluble crosslinkable oligomer to prepare a polyvinyl alcohol mixed solution;
The long-main-chain water-soluble crosslinkable high molecular polymer is one or copolymer of polyvinyl alcohol, chitosan oligosaccharide, gelatin, collagen and fibroin;
The short-chain water-soluble crosslinkable oligomer is one or a mixture of glutaraldehyde, trimeric aldehyde, diacid, dianhydride, diepoxy and dicyandiamide;
(2) Introducing clean air into the polyvinyl alcohol mixed solution, and preparing the micro-bubble polyvinyl alcohol mixed solution by controlling the aperture of the micro-airflow diversion module;
(3) Dropwise adding a sulfuric acid solution into the micro-bubble polyvinyl alcohol mixed solution to prepare a low-density cross-linked soft hydrocolloid cavitation-containing supporting structure;
(4) The low-density crosslinked soft water gel cavitation-containing supporting structure body adopts a split-flow micro-airflow decompression method to prepare a microporous wall cavitation supporting structure body;
(5) Adding a composite reinforcing agent into the microporous wall air cavity supporting structure body to prepare a microporous wall air cavity bionic reinforcing interpenetrating network polymer structure body containing a high-connectivity composite layer;
(6) And (3) introducing active oxygen fluid into the high-communication composite layer-containing microporous wall cavitation bionic enhanced interpenetrating network polymer structure to obtain a finished product.
Further, in the step (1), the molecular weight of the long-main-chain water-soluble crosslinkable high-molecular polymer is 5000-30000, the molecular weight of the short-chain water-soluble crosslinkable low-molecular polymer is 50-3000, the mixing temperature is 20-35 ℃, and the mass ratio of the long-main-chain water-soluble crosslinkable high-molecular polymer to the short-chain water-soluble crosslinkable low-molecular polymer is 1-10.
Further, the long-main-chain water-soluble cross-linkable high molecular polymer is polyvinyl alcohol, and the short-chain water-soluble cross-linkable oligomer is glutaraldehyde.
Further, in the step (2), the flow speed of the clean air is 30-150cm/min, the flow quantity is that the aperture of the micro-air flow splitting module is 100 mu m, 500 mu m and 750 mu m respectively, the spacing distance of the three micro-air flow splitting modules is 1-10cm, and the mixing is carried out by adopting annular stepping and using 5000-20000 rpm.
Three types of low-speed micro-airflows are formed by selecting three types of 100 mu m, 500 mu m and 750 mu m to execute, the low-speed micro-airflows are led into the polyvinyl alcohol mixed solution, micro-bubbles with a plurality of sizes can be generated by adopting micro-flow channels with different apertures, the average aperture diameters are respectively 100-200, 300-500 and 900-1500 mu m, the bubbles can be uniformly dispersed in the polyvinyl alcohol mixed solution after the micro-airflows are led in, the polyvinyl alcohol mixed solution can be divided into three parts, namely a micro-bubble structure main body, a bubble-free solution and a bubble solution interface, wherein the bubble solution interface refers to a gas-liquid interface between the micro-bubble structure main body part and a non-bubble solution main body part.
The invention adopts annular steps, and the micro flow channels formed by micro air flow are utilized to meet the path distribution of the most efficient passing of fluid, thus being particularly suitable for the high-efficiency drainage requirement of drainage materials, generating a bionic drainage microstructure and improving the drainage effect of the finished product.
In the step (3), the mass concentration of the sulfuric acid solution is 1-5%, and the use amount is 1-2% of the mass of the micro-bubble polyvinyl alcohol mixed solution.
Further, in step (4), the pressure is 200-1000psi.
Still further, the pressure is 500psi.
In the invention, 200-1000psi pressure is adopted to match the micro-airflow diversion module to generate the bionic pneumatic micro-airflow to induce the penetration of the low-density crosslinked soft water gel air cavity-containing supporting structure. And forming a plurality of micro-channels connected with a plurality of air pockets on the low-density crosslinked soft water gel air pocket supporting structure, wherein the micro-channels are mainly formed by stirring at a high speed in the step (2) to ensure that the low-density crosslinked soft water gel air pocket supporting structure contains nano bubbles which are dispersed for a plurality of times and are less than 1 mu m in nano-scale size, the nano bubbles vibrate and break under the influence of bionic pneumatic micro-air flow, and hole walls are formed on the surfaces of the air pockets to ensure that the structure is highly communicated, so that the high-communication micro-pore wall air pocket bionic interpenetrating polymer structure is formed.
Further, in the step (5), the compound strengthening agent is one of a mixed water solution of glycerol and glutaraldehyde, a chitosan oligosaccharide, a mixed solution of chitosan oligosaccharide and glutaraldehyde, a mixed solution of chitosan oligosaccharide and trimeric aldehyde, a mixed solution of chitosan oligosaccharide, glycerol and glutaraldehyde.
Further, in the step (5), the reaction temperature is 40-80 ℃.
Further, in the step (5), the reaction temperature was 60 ℃.
The composite enhancer disclosed by the invention can strengthen the microporous wall air cavity structure to form a bionic reinforced composite structural layer. According to the invention, the hydrophilic and hydrophobic properties of the composite reinforcing agent and the microporous wall air cavity supporting structure are controlled through the dosage proportion of the components in the composite reinforcing agent, so that the reinforcing effect is improved.
Further, the compound enhancer is a mixed aqueous solution of glycerol and glutaraldehyde, the mass concentration of the mixed aqueous solution of glycerol and glutaraldehyde is 1-5%, and the mass ratio of the glycerol to the glutaraldehyde is 1:1-10.
Further, in the step (6), the active oxygen fluid is an ozone solution or a hydrogen peroxide water solution or a high oxygen-containing solution, and the concentration of the active oxygen fluid is 1000-5000ppm.
The invention adds active oxygen fluid to form hydrophilic stabilized high-communication microporous wall air pocket to obtain a bionic enhanced interpenetrating polymer network structure containing hydrophilic high-communication microporous wall air pocket.
The beneficial effects of the invention are as follows:
The bionic polyvinyl alcohol structure with the composite layer and the high connectivity microporous wall air pocket prepared by the invention has the advantages of high support, drainage, structural pneumatic performance and the like, and the bionic polyvinyl alcohol structure with the composite layer and the high connectivity microporous wall air pocket presents an open air pocket structure, has a porous network with completely open through holes interconnected, and can improve the drainage performance of products.
Drawings
FIG. 1A microscopic view of the finished product of example 1, in which (A) a 100-fold enlarged view, (B) a 300-fold enlarged view, (C) a 500-fold enlarged view and (D) a 1000-fold enlarged view
FIG. 2 microscopic image of the finished product of comparative example 1, magnified 100 times
FIG. 3 shows a thermal fingerprint of test example 3, in region IV of the thermal fingerprint, (1) the finished product of example 1, (2) rice starch, (3) tapioca starch, (4) potato starch, (5) wheat starch and (+) normal moisture absorption.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1 preparation method of high connectivity microporous wall cavitation bionic polyvinyl alcohol Structure containing composite layer
(1) The polyvinyl alcohol with the number average molecular weight of 5000 and glutaraldehyde short-chain water-soluble crosslinkable oligomer with the molecular weight of 50-3000 are mixed by high-speed homogenizing stirring at the rotation speed of 10000rpm, the mass ratio of the polyvinyl alcohol to the glutaraldehyde is 2:1, and the polyvinyl alcohol mixed solution is formed by uniformly dispersing.
(2) And (3) introducing clean gas with the flow speed of 100cm/min into the polyvinyl alcohol mixed solution through micro-air flow diversion modules, wherein the apertures of the micro-air flow diversion modules are 100 mu m, 500 mu m and 750 mu m respectively, the spacing distance between the three micro-air flow diversion modules is 10cm, the micro-air flow diversion modules are distributed in a ring shape, and the ventilation is finished and the rotation speed of 10000rpm is adopted for dispersion, so that the micro-bubble polyvinyl alcohol mixed solution is prepared.
(3) And (3) dropwise adding the sulfuric acid solution with the mass concentration of 1-5% into the micro-bubble polyvinyl alcohol mixed solution, wherein the use amount is 1-2% of the mass of the micro-bubble polyvinyl alcohol mixed solution, and thus the low-density cross-linked soft water gel air cavity-containing support structure is prepared.
(4) And a step of flow type micro-airflow pressure reduction bionic pneumatic microporous wall cavitation molding, wherein the bionic pneumatic micro-airflow is generated by matching with the micro-airflow flow dividing module through pressure of 500psi to induce penetration of low-density crosslinked soft water gel, so that the microporous wall cavitation supporting structure is prepared.
(5) And adding 1% of a composite strengthening agent into the microporous wall air cavity supporting structure, wherein the composite strengthening agent is a mixed aqueous solution of glycerol and glutaraldehyde, the mass concentration of the mixed aqueous solution of glycerol and glutaraldehyde is 3%, and the mass ratio of the glycerol to the glutaraldehyde is 1:5, so that the microporous wall air cavity bionic strengthening interpenetrating network polymer structure containing the high-pass connectivity composite layer is prepared.
(6) And (3) introducing 1% ozone solution into the high-connectivity composite layer-containing microporous wall air pocket bionic enhanced interpenetrating network polymer structure body, wherein the concentration of the ozone solution is 4000ppm, and thus a finished product is obtained.
Comparative example 1
On the basis of example 1, the clean gas foaming in step (2) was replaced by an air-assisted starch foaming process.
Test example 1
Microstructure analysis of the finished products prepared in example 1 and comparative example 1 by SEM
Referring to fig. 1 and 2, fig. 1 shows the microstructure of the finished graph of example 1, showing an open air pocket structure, a porous network with fully open via interconnections, and a pore size of between about 100 and 150 microns, as shown in fig. 1 (a). Pore walls having pore diameters of 3 to 10 μm are observed in fig. 1 (B).
Fig. 2 shows the microstructure of the finished pattern of comparative example 1, which provides a partially open microstructure, but a partially open microstructure of the through-holes results in a compacted structure with weaker structural support. The weak structural support has poor use effect in clinical use, and the drainage effect is obviously reduced.
Test example 2
The finished product obtained in example 1 was compared with a commercially available finished product in terms of pH, liquid absorption (mL), and residual formaldehyde content (μg/g).
TABLE 1
Experimental results show that the finished product prepared by the method has the composite layer high connectivity microporous wall result, low formaldehyde residue and high liquid absorption.
Test example 3 fingerprint identification
A bionic soft polyvinyl alcohol foam (BA-PVAF) medical drainage material thermal fingerprint evaluation system comprises a thermal fingerprint I region (less than 100 ℃), a thermal fingerprint II region (between 100 ℃ and 300 ℃) and a thermal fingerprint III region (greater than 300 ℃). The weight loss curve obtained by thermogravimetric analysis (TGA) of the bionic soft medical drainage material PVAF can provide information to serve as a basis for identifying the stability of the thermal structure. The extent of residual impurities or thermal degradation products of the material can thus be identified, such as small molecules, solvents, water, residual reagents, residual foaming agents, starches, weak structure molecules and prepolymer molecules, and thermal degradation products thereof.
Referring to fig. 3, the thermal fingerprint I region exhibits only a thermal weight loss of water molecules escaping from the material. The percentage of thermal weight loss in the thermal fingerprint I indicates the water absorption property of the material, for example, the bionic soft medical drainage material has the thermal weight loss of more than 6 percent (normal moisture absorption rate) in the thermal fingerprint I, which indicates that the material has good water absorption and water wettability. Secondly, the TGA and DTG spectra of the bionic PVAF in the thermal fingerprint II region do not show any thermal degradation signal, and suggest that the thermal fingerprint II region has a high thermal stability structure, and any thermogravimetric loss information and DTG curve peak appearing in the thermal fingerprint II region show that the thermal fingerprint II region does not have a thermal stability structure at 300 ℃. Third, in the thermal fingerprint III region, thermal fingerprints displayed by TGA and DTG of the bionic soft medical drainage material PVAF can be observed to have a maximum thermal degradation temperature (Tdmax) higher than 420 ℃ and a narrow peak of a DTG curve, and the thermal fingerprint can be used as the bionic soft medical drainage material to have high thermal structural stability and highly crosslinked and uniform stable polymer structure. The width of the peak of the DTG curve also suggests the purity of the material. Fourth, the thermal fingerprint IV (i) uses the DSC analysis result of the bionic soft medical drainage material PVAF as an index map of the thermal fingerprint IV, and shows that there is no thermal phase change endothermic or exothermic signal below 100, and a gentle curve down at approximately 100 ℃ is attributed to gradual evaporation of water molecules contained in the material. In order to improve the identification efficiency of the high-heat fingerprint identification system in the bionic soft medical drainage material, a plurality of starch sources are selected for DSC result integration, such as rice starch (ii), tapioca starch (iii), potato starch (iv), pea starch (v) and wheat starch (vi), are used as comparison patterns for identifying the traditional foaming process and the bionic foaming process, and the obtained material. Generally, the microstructure of the soft medical drainage material formed by the conventional foaming process of polyvinyl alcohol using starch as a foaming agent may exhibit collapse and close pores, which is disadvantageous for forming high drainage and high support. Therefore, the inclusion of the thermal analysis value and the light absorption value of the starch is more beneficial to rapidly identifying the bionic soft medical drainage material and prompting the characteristic difference of microstructure, drainage and support. The results of the starch thermal analysis are shown in FIG. 3 and Table 2, and each thermal characteristic fingerprint (To, tp, tc) can be used To identify the purity and thermal stability of the soft medical drainage material.
TABLE 2
Test example 4 clinical application
The finished product of the example 1 is applied to the minimally invasive treatment of the nasal cavity, the absorption rate of 15s is 13.6 times, and the water permeability in the negative pressure treatment is 92%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. The preparation method of the high connectivity microporous wall air pocket bionic polyvinyl alcohol structure body containing the composite layer is characterized by comprising the following steps:
(1) Uniformly stirring at a high speed with a rotation speed of 10000rpm to mix polyvinyl alcohol with a number average molecular weight of 5000 and glutaraldehyde short-chain water-soluble crosslinkable oligomer with a molecular weight of 50-3000 according to a mass ratio of 2:1, and uniformly dispersing to form a polyvinyl alcohol mixed solution;
(2) Introducing clean air into the polyvinyl alcohol mixed solution, and preparing the micro-bubble polyvinyl alcohol mixed solution by controlling the aperture of a micro-air flow splitting module, wherein the introducing flow speed of the clean air is 30-150cm/min, the aperture of the micro-air flow splitting module is 100 mu m, 500 mu m and 750 mu m respectively, the spacing distance of the three micro-air flow splitting modules is 1-10cm, the micro-air flow splitting modules are distributed in a ring shape, and the micro-air flow splitting modules are mixed by using 5000-20000rpm after the air flow is introduced;
(3) Dropwise adding a sulfuric acid solution into the micro-bubble polyvinyl alcohol mixed solution to prepare a low-density cross-linked soft hydrocolloid cavitation-containing supporting structure;
(4) The low-density crosslinked soft water gel air cavity supporting structure body adopts a split-flow micro-airflow decompression method to prepare a microporous wall air cavity supporting structure body, and the pressure is 200-1000psi;
(5) Adding a composite reinforcing agent into the microporous wall air cavity supporting structure body to prepare a microporous wall air cavity bionic reinforcing interpenetrating network polymer structure body containing a high-connectivity composite layer;
(6) And (3) introducing active oxygen fluid into the high-communication composite layer-containing microporous wall cavitation bionic enhanced interpenetrating network polymer structure to obtain a finished product.
2. The method for preparing the composite layer-containing high-connectivity microporous wall air pocket bionic polyvinyl alcohol structure according to claim 1, wherein in the step (3), the mass concentration of the sulfuric acid solution is 1-5%, and the use amount is 1-2% of the mass of the micro-bubble polyvinyl alcohol mixed solution.
3. The preparation method of the composite layer-containing high-connectivity microporous wall air pocket bionic polyvinyl alcohol structure body is characterized in that the composite enhancer is a mixed aqueous solution of glycerol and glutaraldehyde, the mass concentration of the mixed aqueous solution of glycerol and glutaraldehyde is 1-5%, and the mass ratio of the glycerol to the glutaraldehyde is 1:1-10.
4. The method for preparing the composite layer-containing high-connectivity microporous wall cavitation bionic polyvinyl alcohol structure according to claim 1, wherein in the step (6), the active oxygen fluid is an ozone solution or a hydrogen peroxide water solution or a high-oxygen-content solution, and the concentration is 1000-5000ppm.
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| CN109762182A (en) * | 2019-01-02 | 2019-05-17 | 大连理工大学 | A kind of high intensity-porous structure polyvinyl alcohol-tannin acid hydrogel preparation method and application |
| CN110183804A (en) * | 2019-06-14 | 2019-08-30 | 西安工程大学 | A kind of polyvinyl alcohol foam material and preparation method thereof |
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| CN114316353A (en) * | 2022-01-20 | 2022-04-12 | 江苏申思生物科技有限公司 | Improved foaming production process method of polyvinyl alcohol sponge |
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| CN109762182A (en) * | 2019-01-02 | 2019-05-17 | 大连理工大学 | A kind of high intensity-porous structure polyvinyl alcohol-tannin acid hydrogel preparation method and application |
| CN110183804A (en) * | 2019-06-14 | 2019-08-30 | 西安工程大学 | A kind of polyvinyl alcohol foam material and preparation method thereof |
| CN113817218A (en) * | 2020-12-25 | 2021-12-21 | 北京蔚蓝天纳科技有限公司 | Biopolymer composite membrane and preparation method thereof |
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