CN115678189B - Preparation method of polyvinyl alcohol (PVA) -based degradable composite material with high mechanical strength - Google Patents
Preparation method of polyvinyl alcohol (PVA) -based degradable composite material with high mechanical strength Download PDFInfo
- Publication number
- CN115678189B CN115678189B CN202211397168.1A CN202211397168A CN115678189B CN 115678189 B CN115678189 B CN 115678189B CN 202211397168 A CN202211397168 A CN 202211397168A CN 115678189 B CN115678189 B CN 115678189B
- Authority
- CN
- China
- Prior art keywords
- pva
- composite material
- polyvinyl alcohol
- solution
- based degradable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 81
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 53
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 17
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 17
- 229920002258 tannic acid Polymers 0.000 claims abstract description 17
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 17
- 229940033123 tannic acid Drugs 0.000 claims abstract description 17
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 17
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 46
- 235000011187 glycerol Nutrition 0.000 description 18
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000013502 plastic waste Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 102000003960 Ligases Human genes 0.000 description 1
- 108090000364 Ligases Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of functional materials, and relates to a preparation method of a polyvinyl alcohol (PVA) based degradable composite material with high mechanical strength. Firstly, 3, 4-dihydroxybenzaldehyde grafted polyvinyl alcohol (g-PVA) is taken as a matrix material, and Tannic Acid (TA) and Fe are added 3+ Ions, which endow the composite material with high-density reversible molecular acting force; and then pouring the obtained g-PVA-Fe-TA complex into a polytetrafluoroethylene mould for drying and molding, and soaking the g-PVA-Fe-TA complex in glycerol/water solutions with different volume ratios to finally obtain the g-PVA-Fe-TA composite material. The degradable g-PVA-Fe-TA composite material obtained by the invention has strong mechanical properties, under the optimal condition, the strain can reach 800 percent, the stress is as high as 18MPa, and the problem of poor mechanical properties of the existing polyvinyl alcohol-based material is well solved.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly provides a preparation method of a PVA-based degradable composite material with high mechanical strength.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Currently, composite materials are increasingly demanded in daily production, and various forms of composite materials are prepared into various products, and the production speed thereof is increased year by year. Traditional composite materials, such as Polyethylene (PE) and polyethylene terephthalate (PET), are extremely inert and take hundreds of years to degrade completely in the natural environment. While PE and PET composites can be degraded by catalytic pyrolysis, highly active microorganisms or expensive synthetases are required to be isolated from the natural environment and degradation generally requires harsh and stringent conditions. Even so, very few composites can be degraded completely efficiently by this method. Currently, more than 1 million tons of plastic waste are discarded into the environment every year worldwide, which causes serious environmental pollution problems. In addition, due to the accumulation of plastic waste in the environment, more and more terrestrial and marine animals are injured, which has a certain influence on the ecological balance of the earth and the food source of human beings. In order to effectively alleviate the serious problems caused by plastic waste accumulation, a large number of students concentrate on the development and preparation of degradation materials.
The most effective way to solve the problem of stacking of composite materials such as plastics is to search for new composite materials to replace traditional composite materials, and the new composite materials need to be completely degraded into environmentally friendly substances in natural environments. Polyvinyl alcohol (PVA) as a novel degradable material has the characteristics of certain mechanical strength, good biocompatibility and no toxicity. In natural environment, PVA is oxidized to generate diketone by hydroxy of PVA, and then carbon-carbon diketone bond is hydrolyzed, so that the PVA can be completely degraded into CO by microorganism 2 And H 2 O. However, the PVA-based polymer material lacks dynamic reversible and high-density strong force inside, so that the mechanical properties of the PVA-based material are limited, and the application of the PVA-based composite material is hindered. Therefore, the preparation of the PVA composite material with high mechanical strength and degradability has important practical significance for expanding the application of the PVA composite material.
Disclosure of Invention
Aiming at the current situation that the PVA composite material in the prior art has insufficient mechanical property, the invention provides a method for grafting PVA (g-PVA for short) by 3, 4-dihydroxybenzaldehyde, and simultaneously introducing Tannic Acid (TA) and Fe into the g-PVA 3+ By high density reversible hydrogen bonding and Fe 3+ And the strong molecular acting force is formed, so that the mechanical property of the PVA composite material is further improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for preparing a polyvinyl alcohol-based degradable composite material having high mechanical strength, comprising:
dissolving PVA in the solution, heating and stirring to obtain PVA solution;
dissolving 3, 4-dihydroxybenzaldehyde in the PVA solution, then adding a TA solution, carrying out ultrasonic treatment under heating and stirring, and then adding p-toluenesulfonic acid for reaction to obtain a reaction solution;
adding ferric trichloride solution into the reaction solution to react to obtain g-PVA-Fe-TA complex solution;
pouring the g-PVA-Fe-TA complex solution into a mould, coating uniformly, solidifying and stripping to obtain a g-PVA-Fe-TA composite material;
soaking the g-PVA-Fe-TA composite material in glycerol/water to obtain the composite material;
based on the raw materials, the invention also researches the composition and the dosage of each component. Through verification, the mass ratio of PVA to 3, 4-dihydroxybenzaldehyde is 8-10: 3-4; the mass ratio of PVA to TA to ferric trichloride is 8-10: 0.02-0.05: 0.06-0.12; the mass ratio of PVA to PTSA is 8-10: and when the weight of the composite material is 0.8-1, the prepared degradable g-PVA-Fe-TA composite material has stronger mechanical property.
In a second aspect of the present invention, there is provided a high mechanical strength polyvinyl alcohol-based degradable composite material prepared by the above method.
In a third aspect, the invention provides the application of the polyvinyl alcohol-based degradable composite material with high mechanical strength in the fields of food, packaging, medicine, construction and machinery.
The beneficial effects of the invention are that
(1) The degradable g-PVA-Fe-TA composite material obtained by the invention has strong mechanical properties, under the optimal condition, the strain can reach 800 percent, the stress is as high as 18MPa, and the problem of poor mechanical properties of the existing polyvinyl alcohol-based material is well solved. The PVA composite material with high mechanical strength and degradability has important practical significance for expanding the application of the PVA composite material.
(2) The preparation method is simple, has strong practicability and is easy to popularize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a flow chart of the preparation of a polyvinyl alcohol (PVA) based degradable composite.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the g-PVA-Fe-TA composite material of example 1 of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the degradation process of the g-PVA-Fe-TA composite material according to example 1 of the present invention.
FIG. 4 is a mechanical property test of the g-PVA-Fe-TA composite material prepared according to example 1 of the present invention: (a) Under manual operation, the g-PVA-Fe-TA composite material can be twisted, bent and pulled up; (b) mechanical property comparison of the four composite materials; (c) The g-PVA-Fe-TA composite material improves the live view diagram of the autoclave; (d) The maximum stresses that the composite of the different components can withstand are compared. (e) And (5) testing the tensile cycle performance of the g-PVA-Fe-TA composite material. Wherein g-PVA means that FeCl is not added 3 And tannic acid, other treatments were as in example 1, g-PVA-TA being unadditized FeCl 3 Other treatments were as in example 1, both of which served as a control.
Fig. 5 uses a texture analyzer to test the tensile force of the composite material. The bottom-up curves correspond to the mechanical property test of the g-PVA-Fe-TA composites of example 1 (glycerol: water=1:0), example 2 (glycerol: water=4:1), example 3 (glycerol: water=1:1), example 4 (glycerol: water=1:4), and example 4 (glycerol: water=0:1), respectively.
FIG. 6 is a graph showing the mechanical properties of the g-PVA-Fe-TA composite material of example 1 of the present invention at different temperatures and storage times.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all 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.
Interpretation of the terms
In the present invention, DMSO means: dimethyl sulfoxide.
PTSA means: p-toluenesulfonic acid.
A preparation method of a PVA-based degradable composite material with high mechanical strength comprises the following steps:
(a) Dissolving 8-10 g of PVA in 140-160 mL of N, N-dimethyl sulfoxide (DMSO) solution, and stirring for 4-6 hours at 70-90 ℃; and then 3-4 g of 3, 4-dihydroxybenzaldehyde is dissolved in the PVA solution under the stirring condition at 70-90 ℃.
(b) And then, dissolving 0.02-0.05 g of TA into 15-20 ml of DMSO solution, dropwise adding the solution, strongly stirring at 70-90 ℃, and carrying out ultrasonic treatment for 10-30 min. And then adding 0.8-1.0 g of p-toluenesulfonic acid (PTSA) into the solution, and reacting for 4-6 hours at 70-90 ℃.
(c) And (3) dropwise adding a DMSO solution (1.5-2.0 ml, 40-60 mg/ml) of ferric trichloride into the reaction solution, stirring for 30-60 minutes at 70-90 ℃, slowly pouring the g-PVA-Fe-TA complex solution into a polytetrafluoroethylene mold, and uniformly coating.
(d) And (3) after drying at 25-50 ℃ for 24-36 hours, manually stripping the complete g-PVA-Fe-TA composite material from the glass plate. And finally, soaking the g-PVA-Fe-TA composite material in glycerol/water for 24-36 hours.
In some embodiments, 9.5 g of PVA is dissolved in DMSO of 158 mL as described in step A and stirred at 90℃for 5 h.
In some embodiments, 3.29 g of 3, 4-dihydroxybenzaldehyde is dissolved in the PVA solution with stirring at 80℃as described in step (a).
In some embodiments, step (b) is performed by dissolving 0.025 g TA in 19 ml DMSO solution and adding dropwise to the solution, stirring vigorously at 80℃and sonicating for 10 min.
In some embodiments, step (b) adds 0.81 g PTSA to the solution and reacts at 80 ℃ for 6h.
In some embodiments, step (c) is performed by dropping a DMSO solution of ferric trichloride (1.90 ml, 50.0 mg/ml) into the reaction solution and stirring at 80℃for 30 minutes.
In some embodiments, the complete g-PVA-Fe-TA composite is manually peeled from the polytetrafluoroethylene mold 36 hours after the 50℃drying of step (d).
In some embodiments, step (d) is performed by immersing the g-PVA-Fe-TA composite material in glycerol/water for 36 hours.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
Example 1
A preparation method of a PVA-based degradable composite material with high mechanical strength comprises the following steps:
first, 9.50 g of PVA was dissolved in 158 and mL of DMSO and stirred at 90℃for 5 h; then 3.29 g of 3, 4-dihydroxybenzaldehyde was dissolved in the PVA solution with stirring at 80 ℃. Subsequently, 0.025 g of TA was dissolved in 19 ml of DMSO solution and added dropwise to the above solution, with vigorous stirring at 80℃and ultrasound for 10 min. After this, 0.81 g of PTSA was added to the solution and reacted at 80℃for 6h. Ferric trichloride in DMSO (1.90 ml, 50.0 mg/ml) was added dropwise to the reaction solution, and after stirring at 80℃for 30 minutes, the g-PVA-Fe-TA complex solution was poured slowly into a polytetrafluoroethylene mold and coated uniformly. After 36 hours of drying at 50 ℃, the complete g-PVA-Fe-TA composite material was manually peeled from the polytetrafluoroethylene mold. Finally, the g-PVA-Fe-TA composite material is soaked in glycerin/water for 36 hours, wherein the volume ratio of glycerin to water is 1:0.
example 2
A preparation method of a PVA-based degradable composite material with high mechanical strength comprises the following steps:
first, 9.50 g of PVA was dissolved in 158 and mL of DMSO and stirred at 90℃for 5 h; then 3.29 g of 3, 4-dihydroxybenzaldehyde was dissolved in the PVA solution with stirring at 80 ℃. Subsequently, 0.025 g of TA was dissolved in 19 ml of DMSO solution and added dropwise to the above solution, with vigorous stirring at 80℃and ultrasound for 10 min. After this, 0.81 g of PTSA was added to the solution and reacted at 80℃for 6h. Ferric trichloride in DMSO (1.90 ml, 50.0 mg/ml) was added dropwise to the reaction solution, and after stirring at 80℃for 30 minutes, the g-PVA-Fe-TA complex solution was poured slowly into a polytetrafluoroethylene mold and coated uniformly. After 36 hours of drying at 50 ℃, the complete g-PVA-Fe-TA composite was manually peeled from the glass plate. Finally, the g-PVA-Fe-TA composite material is soaked in glycerin/water for 36 hours, wherein the volume ratio of glycerin to water is 4:1.
example 3
A preparation method of a PVA-based degradable composite material with high mechanical strength comprises the following steps:
first, 9.50 g of PVA was dissolved in 158 and mL of DMSO and stirred at 90℃for 5 h; 3.29 g of 3, 4-dihydroxybenzaldehyde are then dissolved in the PVA solution with stirring at 80 ℃. Subsequently, 0.025 g of TA was dissolved in 19 ml of DMSO solution and added dropwise to the above solution, with vigorous stirring at 80℃and ultrasound for 10 min. After this, 0.81 g of PTSA was added to the solution and reacted at 80℃for 6h. Ferric trichloride in DMSO (1.90 ml, 50.0 mg/ml) was added dropwise to the reaction solution, and after stirring at 80℃for 30 minutes, the g-PVA-Fe-TA complex solution was poured slowly into a polytetrafluoroethylene mold and coated uniformly. After 36 hours of drying at 50 ℃, the complete g-PVA-Fe-TA composite material was manually peeled from the polytetrafluoroethylene mold. Finally, the g-PVA-Fe-TA composite material is soaked in glycerin/water for 36 hours, wherein the volume ratio of glycerin to water is 1:1.
example 4
A preparation method of a PVA-based degradable composite material with high mechanical strength comprises the following steps:
first, 9.50 g of PVA was dissolved in 158 and mL of DMSO and stirred at 90℃for 5 h; then 3.29 g of 3, 4-dihydroxybenzaldehyde was dissolved in the PVA solution with stirring at 80 ℃. Subsequently, 0.025 g of TA was dissolved in 19 ml of DMSO solution and added dropwise to the above solution, with vigorous stirring at 80℃and ultrasound for 10 min. After this, 0.81 g of PTSA was added to the solution and reacted at 80℃for 6h. Ferric trichloride in DMSO (1.90 ml, 50.0 mg/ml) was added dropwise to the reaction solution, and after stirring at 80℃for 30 minutes, the g-PVA-Fe-TA complex solution was poured slowly into a polytetrafluoroethylene mold and coated uniformly. After 36 hours of drying at 50 ℃, the complete g-PVA-Fe-TA composite material was manually peeled from the polytetrafluoroethylene mold. Finally, the g-PVA-Fe-TA composite material is soaked in glycerin/water for 36 hours, wherein the volume ratio of glycerin to water is 1:4.
example 5
A preparation method of a PVA-based degradable composite material with high mechanical strength comprises the following steps:
first, 9.50 g of PVA was dissolved in 158 and mL of DMSO and stirred at 90℃for 5 h; then 3.29 g of 3, 4-dihydroxybenzaldehyde was dissolved in the PVA solution with stirring at 80 ℃. Subsequently, 0.025 g of TA was dissolved in 19 ml of DMSO solution and added dropwise to the above solution, with vigorous stirring at 80℃and ultrasound for 10 min. After this, 0.81 g of PTSA was added to the solution and reacted at 80℃for 6h. Ferric trichloride in DMSO (1.90 ml, 50.0 mg/ml) was added dropwise to the reaction solution, and after stirring at 80℃for 30 minutes, the g-PVA-Fe-TA complex solution was poured slowly into a polytetrafluoroethylene mold and coated uniformly. After 36 hours of drying at 50 ℃, the complete g-PVA-Fe-TA composite material was manually peeled from the polytetrafluoroethylene mold. Finally, the g-PVA-Fe-TA composite material is soaked in glycerin/water for 36 hours, wherein the volume ratio of glycerin to water is 0:1.
the PVA-based degradable composite material with high mechanical strength is characterized and tested, and the results are shown in figures 1 to 6, so that the PVA-based degradable composite material prepared by the invention can reach 800% of strain and 18MPa of stress under the optimal condition, and the problem of poor mechanical property of the existing polyvinyl alcohol-based material is well solved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for preparing a polyvinyl alcohol-based degradable composite material with high mechanical strength, which is characterized by comprising the following steps:
(1) Dissolving PVA in the solution, heating and stirring to obtain PVA solution;
(2) Dissolving 3, 4-dihydroxybenzaldehyde in the PVA solution, adding a tannic acid TA solution, performing ultrasonic treatment under heating and stirring, and then adding p-toluenesulfonic acid PTSA for reaction to obtain a reaction solution;
(3) Adding ferric trichloride solution into the reaction solution to react to obtain g-PVA-Fe-TA complex solution;
(4) Pouring the g-PVA-Fe-TA complex solution into a mould, coating uniformly, solidifying and stripping to obtain a g-PVA-Fe-TA composite material;
(5) Soaking the g-PVA-Fe-TA composite material in glycerol to obtain the composite material;
the mass ratio of PVA to 3, 4-dihydroxybenzaldehyde is 8-10: 3-4;
the mass ratio of PVA, tannic acid TA and ferric trichloride is 8-10: 0.02-0.05: 0.06-0.12;
the mass ratio of PVA to p-toluenesulfonic acid PTSA is 8-10: 0.8-1;
the specific conditions of heating and stirring in the step (1) are that stirring is carried out for 4-6 hours at the temperature of 70-90 ℃.
2. The method for preparing the high-mechanical-strength polyvinyl alcohol-based degradable composite material according to claim 1, wherein the mass ratio of PVA to 3, 4-dihydroxybenzaldehyde is 9-9.5: 3.2-3.5.
3. The method for preparing the high-mechanical-strength polyvinyl alcohol-based degradable composite material according to claim 1, wherein the mass ratio of PVA, tannic acid TA and ferric trichloride is 9-9.5: 0.025 to 0.030:0.09 to 0.10.
4. The method for preparing the high-mechanical-strength polyvinyl alcohol-based degradable composite material according to claim 1, wherein the mass ratio of PVA to p-toluenesulfonic acid PTSA is 9-9.5: 0.8 to 0.85.
5. The method for preparing the high-mechanical-strength polyvinyl alcohol-based degradable composite material according to claim 1, wherein the high-mechanical-strength polyvinyl alcohol-based degradable composite material is subjected to strong stirring at 70-90 ℃ and ultrasonic treatment for 10-30 min.
6. The method for preparing a high mechanical strength polyvinyl alcohol-based degradable composite material according to claim 1, wherein the curing condition is drying at 25-50 ℃ for 24-36 hours.
7. The method for preparing the high-mechanical-strength polyvinyl alcohol-based degradable composite material according to claim 1, wherein the composite material is soaked in glycerol for 24-36 hours.
8. A high mechanical strength polyvinyl alcohol-based degradable composite material prepared by the method of any one of claims 1-7.
9. Use of the high mechanical strength polyvinyl alcohol based degradable composite material according to claim 8 in the fields of food, packaging, medicine, construction, machinery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211397168.1A CN115678189B (en) | 2022-11-09 | 2022-11-09 | Preparation method of polyvinyl alcohol (PVA) -based degradable composite material with high mechanical strength |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211397168.1A CN115678189B (en) | 2022-11-09 | 2022-11-09 | Preparation method of polyvinyl alcohol (PVA) -based degradable composite material with high mechanical strength |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115678189A CN115678189A (en) | 2023-02-03 |
| CN115678189B true CN115678189B (en) | 2024-02-27 |
Family
ID=85049426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211397168.1A Active CN115678189B (en) | 2022-11-09 | 2022-11-09 | Preparation method of polyvinyl alcohol (PVA) -based degradable composite material with high mechanical strength |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115678189B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372595A (en) * | 2021-07-31 | 2021-09-10 | 贵州省材料产业技术研究院 | Rare earth metal complexing polyvinyl alcohol film and preparation method thereof |
| CN114957894A (en) * | 2021-02-18 | 2022-08-30 | 吉林大学 | Polyvinyl alcohol-based composite material and preparation method, application and recovery method thereof |
-
2022
- 2022-11-09 CN CN202211397168.1A patent/CN115678189B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957894A (en) * | 2021-02-18 | 2022-08-30 | 吉林大学 | Polyvinyl alcohol-based composite material and preparation method, application and recovery method thereof |
| CN113372595A (en) * | 2021-07-31 | 2021-09-10 | 贵州省材料产业技术研究院 | Rare earth metal complexing polyvinyl alcohol film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 仿贻贝类含儿茶酚改性聚乙烯醇黏附凝胶的合成;杨潇 等;《功能材料》;第第46卷卷(第第15期期);第15016-15020页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115678189A (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lai et al. | Surface characterization of TEMPO‐oxidized bacterial cellulose | |
| Singh et al. | A review on Borassus flabellifer lignocellulose fiber reinforced polymer composites | |
| Zhang et al. | Starch-based rehealable and degradable bioplastic enabled by dynamic imine chemistry | |
| Hossen et al. | Effect of clay content on the morphological, thermo-mechanical and chemical resistance properties of propionic anhydride treated jute fiber/polyethylene/nanoclay nanocomposites | |
| CN108948690A (en) | A kind of polylactic acid-lignin-starch composite material and preparation method thereof | |
| CN111704788A (en) | Fully-biodegradable cotton swab stick and preparation method thereof | |
| He et al. | Microcrystalline cellulose as reactive reinforcing fillers for epoxidized soybean oil polymer composites | |
| Robledo-Ortíz et al. | Lignocellulosic materials as reinforcement of polyhydroxybutyrate and its copolymer with hydroxyvalerate: A review | |
| Won et al. | Mechanical properties and biodegradability of the kenaf/soy protein isolate-PVA biocomposites | |
| CN106279979A (en) | A kind of Graphene is combined shock resistance PP plastics and preparation method thereof | |
| CN110964332B (en) | Hyperbranched polyester toughened and reinforced high-strength recyclable soybean protein film and preparation method thereof | |
| CN115678189B (en) | Preparation method of polyvinyl alcohol (PVA) -based degradable composite material with high mechanical strength | |
| CN108892793A (en) | A kind of preparation method of degradable green high-barrier high grade of transparency nano cellulose composite film | |
| Martínez-Herrera et al. | Integration of Agave plants into the polyhydroxybutyrate (PHB) production: A gift of the ancient Aztecs to the current bioworld | |
| CN108948679A (en) | A kind of lignin modification starch base PBAT biodegrade membrane material and preparation method thereof | |
| CN112625347A (en) | Low-odor, high-performance and environment-friendly polypropylene composite material and preparation method thereof | |
| Li et al. | Surface treatment of single sisal fibers with bacterial cellulose and its enhancement in fiber-polymer adhesion properties | |
| Madu et al. | Effects of fiber volume fraction and curing time on impact–hardness strength properties of areca fibers reinforced polyester thermoset composites | |
| CN111849177A (en) | Full-biodegradable material | |
| CN113214619A (en) | Microfibrillated cellulose and polylactic acid composite material and preparation method thereof | |
| CN112280107A (en) | Biodegradable polyolefin plastic composite additive in open land environment and preparation method and application thereof | |
| CN101225191B (en) | Tape casting method for preparing full biological degradable containing konjac glucomannan | |
| Sekhar et al. | Biodegradation of emu feather fiber reinforced epoxy composites | |
| CN112661638B (en) | Toughening intermediate, preparation method thereof and toughened mosquito-repellent high-molecular biodegradable composite material for 3D printing | |
| CN115558141B (en) | High-toughness high-antibacterial degradable composite film based on cellulose nano-alkene, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |