CN110240774B - High-strength lignin/polyvinyl alcohol composite conductive hydrogel and preparation method thereof - Google Patents
High-strength lignin/polyvinyl alcohol composite conductive hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN110240774B CN110240774B CN201910542444.0A CN201910542444A CN110240774B CN 110240774 B CN110240774 B CN 110240774B CN 201910542444 A CN201910542444 A CN 201910542444A CN 110240774 B CN110240774 B CN 110240774B
- Authority
- CN
- China
- Prior art keywords
- lignin
- hydrogel
- polyvinyl alcohol
- soaking
- parts
- 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
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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- 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
-
- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and discloses a high-strength lignin/polyvinyl alcohol composite conductive hydrogel and a preparation method thereof. The composite conductive hydrogel is lignin-enhanced PVA hydrogel, and specifically is high-strength lignin/polyvinyl alcohol composite conductive hydrogel which is obtained by sequentially soaking water-soluble silver salt solution after lignin is mixed with PVA to prepare gel A and reducing the gel A by using a reducing agent. According to the invention, lignin is added into the polyvinyl alcohol hydrogel, and the lignin is self-assembled to form a nano microphase separation structure, and simultaneously, Ag is promoted to be adsorbed+Adsorption of (3); the reducing agent adsorbs Ag on the outer surface of the hydrogel+Reducing to form compact nano silver particle clusters on the surface of the hydrogel. The compact external structure and the loose internal structure enable the hydrogel to have ultrahigh mechanical strength and toughness, excellent conductivity and antibacterial performance, and the tensile strength of the hydrogel is up to 13.0 MPa; the elongation at break reaches up to 1500 percent; the conductivity is as high as 10.126S/m.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to high-strength lignin/polyvinyl alcohol composite conductive hydrogel and a preparation method thereof.
Background
Hydrogels, a swellable body with a three-dimensional polymer network structure, formed by physical or chemical crosslinking, contain a large amount of water but are insoluble in water [ science, 2017,356, (6337).]Has a series of advantages including softness, rich water content, good biocompatibility and the like. Hydrogels are widely used in the fields of biomedicine, tissue engineering, flexible electronics, sensors, etc. [ Adv mater, 2016,28, (22):4497.]. However, the mechanical properties of the conventional hydrogel are poor, and the potential application of the conventional hydrogel in the field of flexible devices is greatly limited. In recent years, a large number of newspapersThe mechanical strength of the hydrogel is enhanced by constructing an energy sacrificial bond, a physical double network, electrostatic interaction, hydrogen bond interaction and the like, but the high-strength hydrogel with excellent conductivity is rarely reported. Chen et al [ adv.Funct.Mater.2019,29, (1):1806220.]Preparing ion conductive hydrogel with high elasticity, high modulus and high conductivity by embedding hydroxypropyl cellulose (HPC) in polyvinyl alcohol (PVA) and soaking in salt solution, wherein the tensile stress of the conductive hydrogel is 1.3MPa, and the toughness is 5.8MJ/m3The ionic conductivity reaches 3.4S/m. Lei et al [ Nature communications, 2018,9.]The supermolecule self-healing bionic skin with wide mechanical properties and various sensory abilities is prepared, but the mechanical strength of the hydrogel is very low. The search for functional hydrogels that combine good mechanical properties and high electrical conductivity remains a great challenge.
Polyvinyl alcohol (PVA) contains a large number of hydroxyl groups and can be crosslinked to form hydrogels either physically or chemically. Due to good biocompatibility and biodegradability, the composite material has great potential application value and is expected to be widely applied to various fields. However, the mechanical properties of PVA hydrogel are poor, so that the popularization and application of PVA hydrogel are greatly limited. In the literature, inorganic materials such as graphite oxide, calcium carbonate, clay, graphene and ammonium sulfate ions are used in a large amount to enhance the strength of hydrogel [ Adv mater, 2015,27, (7):1294 ], so that the biocompatibility and biodegradability of the hydrogel are remarkably reduced.
Lignin is the second largest biomass resource next to cellulose in plants, is a natural high molecular compound with an aromatic ring structure, and is known as one of the most abundant green resources which can be utilized by human in 21 st century [ ChemRev 2016,116, (4):2275 ]. Due to the properties of low cost, no toxicity, high thermal stability, biodegradability, ultraviolet absorption and the like, the lignin composite material attracts great attention of researchers. The lignin contains rich oxygen-containing functional groups (hydroxyl, carboxyl and the like), can not only form hydrogen bond action with PVA chains, but also chelate metal ions, and the introduction of green lignin for enhancing the biodegradable PVA hydrogel is a feasible method for preparing the high-performance multifunctional green hydrogel. However, the enhancement effect of the hydrogel due to the self-aggregation of the lignin is limited, and the effective antibacterial performance cannot be endowed by simply introducing the lignin.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a high-strength lignin/polyvinyl alcohol composite conductive hydrogel.
The invention also aims to provide a preparation method of the high-strength lignin/polyvinyl alcohol composite conductive hydrogel.
The purpose of the invention is realized by the following scheme:
a high-strength lignin/polyvinyl alcohol composite conductive hydrogel is a lignin-enhanced PVA hydrogel, and specifically is prepared by mixing lignin with PVA to prepare a gel A, sequentially soaking in a water-soluble silver salt solution, and reducing by a reducing agent to obtain the high-strength lignin/polyvinyl alcohol composite conductive hydrogel.
The mass ratio of PVA to lignin is preferably 2:1 to 10: 1.
The mass concentration of PVA in the gel A is preferably 4.5 to 30%.
The gel prepared by mixing the lignin and the PVA can be prepared by mixing and dispersing the lignin and the PVA in a solvent, stirring for 1-6h at 70-140 ℃, casting and molding, and then obtaining the composite hydrogel by a freezing-thawing method or a solvent exchange method. More preferably at 80-120 deg.C for 1-6 h. The stirring rate is preferably 100-. The solvent is preferably a mixed solvent of water and dimethyl sulfoxide, and the volume ratio of the mixed solvent to the dimethyl sulfoxide is 4:1-1: 4.
The casting molding process conditions may be conventional casting molding process conditions in the art, and are well known to those skilled in the art. The freeze-thaw method or the solvent exchange method is a conventional method for preparing a hydrogel and is well known to those skilled in the art.
The soaking time is preferably 1-6 h.
The concentration of the water-soluble silver salt solution can be 0.01-1 mol/L. The water soluble silver salt may be selected from silver nitrate and the like.
The reduction by the reducing agent can be realized by soaking the soaked hydrogel in a reducing agent solution, and more specifically, the soaked hydrogel can be soaked in a reducing agent solution for 1-5 hours.
The reducing agent can be sodium citrate, sodium borohydride, dopamine, ascorbic acid and the like.
The concentration of the reducing agent solution is preferably 0.1 to 2 mol/L.
The PVA used in the present invention is an alcoholysis product of polyvinyl acetate known in the art, preferably having an alcoholysis degree of 85% or more and a molecular weight of 3000 or more.
The lignin used in the present invention can be, but is not limited to, at least one of alkali lignin obtained by alkali pulping in paper industry, enzymatic lignin extracted from ethanol prepared by fermenting lignocellulose, organosolv lignin extracted from lignocellulose by organosolv method, or lignosulfonate (including calcium lignosulfonate, sodium lignosulfonate, and lignosulfonic acid) as a byproduct in sulfite pulping.
According to the invention, lignin is added into the polyvinyl alcohol hydrogel, the amphiphilic lignin forms a nano microphase separation structure in the polyvinyl alcohol hydrogel through self-assembly, and simultaneously the lignin promotes the polyvinyl alcohol hydrogel to carry out Ag+Adsorption of (3); further introducing a reducing agent to adsorb Ag on the outer surface of the hydrogel+Reducing to form compact nano silver particle clusters on the surface of the hydrogel. The compact external structure and the loose internal structure enable the hydrogel to have ultrahigh mechanical strength and toughness, and meanwhile, the shell formed by the nano silver particle clusters also endows the hydrogel with excellent conductivity and antibacterial performance.
The invention can obtain hydrogel with different mechanical properties and conductive properties by adjusting the dosage of lignin in the hydrogel and the concentration of the water-soluble silver salt and the reducing agent solution, and the tensile strength of the hydrogel can reach 0.1-13.0MPa, and can reach 13.0MPa at most; the elongation at break can reach 461-1500 percent, and the highest elongation at break can reach 1500 percent; the conductivity can reach 0.009-10.126S/m.
The invention also provides a preparation method of the high-strength lignin/polyvinyl alcohol composite conductive hydrogel, which comprises the following steps:
(1) mixing PVA and lignin, adding the mixture into a solvent, uniformly dispersing, stirring for 1-6h at 70-140 ℃, casting and molding, and obtaining the composite hydrogel by a freezing-thawing method or a solvent exchange method;
(2) soaking the composite hydrogel obtained in the step (1) in a water-soluble silver salt solution for 1-6 h;
(3) and (3) soaking the soaked hydrogel in a reducing agent solution for 1-5 hours to obtain the high-strength lignin/polyvinyl alcohol composite conductive hydrogel.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the lignin used in the invention is alkali lignin obtained by alkali pulping in the paper industry or enzymolysis lignin extracted from ethanol prepared by fermenting lignocellulose or lignin or lignosulfonate byproduct extracted from lignocellulose by an organic solvent method in pulping by lignin or sulfite, the raw material of the lignosulfonate is derived from biomass resources, and the lignosulfonate composite hydrogel has environmental friendliness and biodegradability.
2. According to the invention, amphipathic lignin is added to form a nano microphase separation structure through hydrophobic self-assembly in a polyvinyl alcohol hydrogel matrix; meanwhile, the chelation of lignin promotes the polyvinyl alcohol composite hydrogel to Ag+Adsorption of (3); reducing Ag adsorbed on the outer surface of the hydrogel by further introducing a reducing agent+And forming compact nano silver particle clusters on the surface of the hydrogel. The compact external structure and the loose internal structure of the hydrogel impart it with ultra-high mechanical strength and toughness.
3. The lignin/polyvinyl alcohol composite hydrogel prepared by the invention also has excellent conductivity and antibacterial activity.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available. The using amount of each component is g and mL in parts by mass.
Example 1
Taking 4.5 parts by mass of polyvinyl alcohol and 0.5 part by mass of lignin, and adding 72.4 parts by volume of water; 18.1 volume parts of DMSO solution, heating at 70 ℃, mechanically stirring at 100rpm for 1h, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.01mol/L silver nitrate solution for 1h, and then soaking in 0.1mol/L sodium citrate for 1h to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 2
Adding 66.15 parts by volume of water into 5 parts by mass of polyvinyl alcohol and 0.5 part by mass of lignin; 28.35 volume parts of DMSO solution, heating at 80 ℃, mechanically stirring at 120rpm for 2 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.02mol/L silver nitrate solution for 2 hours, and then soaking in 0.2mol/L dopamine for 2 hours, thus finally obtaining the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 3
Adding 55.8 parts by volume of water into 5.5 parts by mass of polyvinyl alcohol and 1.5 parts by mass of lignin; and (2) heating the DMSO solution by 37.2 volume parts at 90 ℃, mechanically stirring at 300rpm for 3 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.03mol/L silver nitrate solution for 3 hours, and then soaking in 0.3mol/L sodium citrate for 3 hours to finally obtain a finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 4
Taking 6 parts by mass of polyvinyl alcohol and 2 parts by mass of lignin, and adding 46 parts by volume of water; and (2) mechanically stirring 46 parts by volume of DMSO solution at the heating temperature of 100 ℃ for 4h at 400rpm, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.04mol/L silver nitrate solution for 3h, and then soaking in 0.4mol/L sodium borohydride for 4h to finally obtain a finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 5
Taking 6.5 parts by mass of polyvinyl alcohol and 2.5 parts by mass of lignin, and adding 36.4 parts by volume of water; 54.6 parts by volume of DMSO solution, heating at 110 ℃, mechanically stirring at 500rpm for 5 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.05mol/L silver nitrate solution for 5 hours, and then soaking in 0.5mol/L sodium citrate for 5 hours to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 6
Taking 7 parts by mass of polyvinyl alcohol and 5 parts by mass of lignin, and adding 26.4 parts by volume of water; 61.6 volume parts of DMSO solution, heating at 120 ℃, mechanically stirring at 600rpm for 6 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the exchanged composite hydrogel in 0.06mol/L silver nitrate solution for 6 hours, and then soaking in 0.5mol/L ascorbic acid for 5 hours to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is byproduct sodium lignosulfonate produced in sulfite pulping.
Example 7
Taking 8 parts by mass of polyvinyl alcohol and 3.5 parts by mass of lignin, and adding 17.7 parts by volume of water; 70.8 volume parts of DMSO solution, mechanically stirring at 800rpm for 2 hours at the heating temperature of 140 ℃, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.07mol/L silver nitrate solution for 2 hours, and then soaking in 0.6mol/L sodium citrate for 2 hours to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 8
Adding 69.6 parts by volume of water into 9 parts by mass of polyvinyl alcohol and 4 parts by mass of lignin; and (2) heating 17.4 parts by volume of DMSO solution at 140 ℃, mechanically stirring at 800rpm for 2 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, soaking the composite hydrogel after solvent exchange in 0.08mol/L silver nitrate solution for 1 hour, and soaking in 0.7mol/L dopamine for 2 hours to finally obtain a finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 9
Adding 59.85 parts by volume of water into 10 parts by mass of polyvinyl alcohol and 4.5 parts by mass of lignin; 25.65 parts by volume of DMSO solution, heating at 70 ℃, mechanically stirring at 300rpm for 1h, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.09mol/L silver nitrate solution for 2h, and then soaking in 0.8mol/L sodium citrate for 2h to finally obtain the finished product of the lignin/polyvinyl alcohol composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 10
Taking 11 parts by mass of polyvinyl alcohol and 5 parts by mass of lignin, and adding 50.4 parts by volume of water; and (2) mechanically stirring 33.6 parts by volume of DMSO solution at the heating temperature of 120 ℃ for 3 hours at 900rpm, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.10mol/L silver nitrate solution for 5 hours, and then soaking in 0.9mol/L sodium borohydride for 5 hours to finally obtain a finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 11
Taking 12 parts by mass of polyvinyl alcohol and 5.5 parts by mass of lignin, and adding 41.25 parts by volume of water; 41.25 parts by volume of DMSO solution, heating at 130 ℃, mechanically stirring at 1000rpm for 6 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.2mol/L silver nitrate solution for 6 hours, and then soaking in 1.0mol/L sodium citrate for 2 hours to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 12
Taking 13 parts by mass of polyvinyl alcohol and 6 parts by mass of lignin, and adding 32.4 parts by volume of water; 48.6 parts by volume of DMSO solution, heating at 140 ℃, mechanically stirring at 500rpm for 4 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.3mol/L silver nitrate solution for 1 hour, and then soaking in 1.1mol/L ascorbic acid for 2 hours to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 13
Taking 14 parts by mass of polyvinyl alcohol and 6.5 parts by mass of lignin, and adding 23.85 parts by volume of water; 55.65 volume parts of DMSO solution, heating at 70 ℃, mechanically stirring at 300rpm for 6h, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.04mol/L silver nitrate solution for 2h, and then soaking in 1.5mol/L sodium citrate for 5h to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is lignosulfonic acid, a by-product of sulfite pulping.
Example 14
Taking 15 parts by mass of polyvinyl alcohol and 7 parts by mass of lignin, and adding 15.6 parts by volume of water; 62.4 volume parts of DMSO solution, heating at 110 ℃, mechanically stirring at 100rpm for 2h, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.03mol/L silver nitrate solution for 6h, and then soaking in 1.8mol/L dopamine for 4h to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is alkali lignin obtained by alkali pulping in the paper industry.
Example 15
Taking 17 parts by mass of polyvinyl alcohol and 7.5 parts by mass of lignin, and adding 60.4 parts by volume of water; 15.1 volume parts of DMSO solution, heating at 70 ℃, mechanically stirring at 200rpm for 3 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then placing the composite hydrogel after solvent exchange in 0.50mol/L silver nitrate solution for soaking for 5 hours, and then placing in 1.8mol/L sodium citrate for soaking for 2 hours, thus finally obtaining the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is alkali lignin obtained by alkali pulping in the paper industry.
Example 16
Taking 18 parts by mass of polyvinyl alcohol and 8 parts by mass of lignin, and adding 51.8 parts by volume of water; 22.2 volume parts of DMSO solution, mechanically stirring at 500rpm for 5 hours at the heating temperature of 130 ℃, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.70mol/L silver nitrate solution for 5 hours, and then soaking in 2.0mol/L sodium citrate for 3 hours to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is a byproduct calcium lignosulfonate produced in sulfite pulping.
Example 17
Taking 19 parts by mass of polyvinyl alcohol and 9 parts by mass of lignin, and adding 43.2 parts by volume of water; 28.8 volume parts of DMSO solution, heating at 80 ℃, mechanically stirring at 1000rpm for 2h, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.9mol/L silver nitrate solution for 6h, and then soaking in 1.5mol/L sodium borohydride for 4h to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is byproduct sodium lignosulfonate produced in sulfite pulping.
Example 18
Taking 20 parts by mass of polyvinyl alcohol and 5 parts by mass of lignin, and adding 37.5 parts by volume of water; and (2) heating 37.5 parts by volume of DMSO solution at 140 ℃, mechanically stirring at 150rpm for 3 hours, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 1mol/L silver nitrate solution for 5 hours, and then soaking in 0.5mol/L sodium citrate for 4 hours to finally obtain a finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is a byproduct calcium lignosulfonate produced in sulfite pulping.
Example 19
Taking 23 parts by mass of polyvinyl alcohol and 10 parts by mass of lignin, and adding 26.8 parts by volume of water; 40.2 volume parts of DMSO solution, heating at 100 ℃, mechanically stirring at 200rpm for 2h, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 1.0mol/L silver nitrate solution for 6h, and then soaking in 2.0mol/L ascorbic acid for 5h to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is byproduct sodium lignosulfonate produced in sulfite pulping.
Example 20
Taking 20 parts by mass of polyvinyl alcohol and 15 parts by mass of lignin, and adding 19.5 parts by volume of water; and (2) mechanically stirring 45.5 parts by volume of DMSO solution at the heating temperature of 110 ℃ for 1h at 800rpm, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.5mol/L silver nitrate solution for 3h, and then soaking in 0.5mol/L sodium citrate for 5h to finally obtain the finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is a byproduct calcium lignosulfonate produced in sulfite pulping.
Example 21
Taking 30 parts by mass of polyvinyl alcohol and 5 parts by mass of lignin, and adding 13 parts by volume of water; and (2) mechanically stirring 52 parts by volume of DMSO solution at the heating temperature of 120 ℃ for 6h at 600rpm, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12h, thawing for 2h, soaking the thawed composite hydrogel in deionized water for 24h for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.60mol/L silver nitrate solution for 6h, and then soaking in 1.9mol/L sodium citrate for 4h to finally obtain a finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is alkali lignin obtained by alkali pulping in the paper industry.
Example 22
Taking 30 parts by mass of polyvinyl alcohol and 10 parts by mass of lignin, and adding 48 parts by volume of water; and (2) mechanically stirring 12 parts by volume of DMSO solution at the heating temperature of 120 ℃ for 4 hours at 500rpm, pouring the fully dissolved mixed solution into a mold, naturally cooling at room temperature, freezing for 12 hours, thawing for 2 hours, soaking the thawed composite hydrogel in deionized water for 24 hours for solvent exchange, then soaking the composite hydrogel after solvent exchange in 0.60mol/L silver nitrate solution for 5 hours, and then soaking in 1.7mol/L sodium borohydride for 3 hours to finally obtain a finished product of the lignin/polyvinyl alcohol/silver composite hydrogel. Wherein the selected lignin is a byproduct calcium lignosulfonate produced in sulfite pulping.
The products of the examples are prepared into sample strips meeting the GBT 1040.3-2006 standard, an MTS universal tester is adopted to test mechanical property data such as tensile strength, compressive strength, breaking tensile rate and the like, a dumbbell-shaped hydrogel sample strip is adopted in the tensile property test, and a cylindrical hydrogel sample is adopted in the compressive property test. The hydrogel conductivity σ was calculated according to the formula σ ═ d/(R · a), where the R value is the resistance of the hydrogel measured by a four-probe detector, a is the cross-sectional area of the hydrogel, and d is the distance between the two probes. The performance results of the lignin/polyvinyl alcohol/silver composite hydrogel are summarized in table 1.
The mechanical property test of the lignin/polyvinyl alcohol/silver composite hydrogel is carried out according to the GB/T1040.3-2006 standard, the thicknesses of 10 random positions among the middle sections of the composite hydrogel are measured by using an electronic digital display caliper, then the average value is taken, and then the tensile strength of the hydrogel is measured by using a universal tester at the tensile speed of 100 mm/min; compression performance test the compression performance of the hydrogel was tested at a compression speed of 50mm/min, 90% compressive strain.
TABLE 1 Properties of Lignin/polyvinyl alcohol/silver composite hydrogels
As can be seen from table 1, examples 1, 6, 18 and 21, to which 5 wt% of lignosulfonic acid, sodium lignosulfonate, calcium lignosulfonate and lignin were added, respectively, have significantly improved elongation at break and tensile strength and toughness, relative to the pure PVA blank control; the addition of lignin can obviously improve the tensile strength, the elongation at break and the absorption energy at break of the hydrogel; the results of the embodiment show that the hydrogel can be effectively reinforced and toughened by adding the lignin and sequentially soaking the silver nitrate solution and the sodium citrate solution; and the electrical conductivity of the hydrogel can be obviously improved by soaking the silver nitrate solution and the sodium citrate solution.
Since the raw materials and blending process used in other examples are similar to those of example 1, the performance of the hydrogels prepared in other examples are similar to the above results, and thus are not repeated.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. The high-strength lignin/polyvinyl alcohol composite conductive hydrogel is characterized by comprising the following steps:
(1) mixing PVA and lignin, adding the mixture into a solvent, uniformly dispersing, stirring for 1-6h at 70-140 ℃, casting and molding, and obtaining the composite hydrogel by a freezing-thawing method or a solvent exchange method; the mass ratio of the PVA to the lignin is 2:1-10: 1;
(2) soaking the composite hydrogel obtained in the step (1) in a water-soluble silver salt solution for 1-6 h; the concentration of the water-soluble silver salt solution is 0.01-1 mol/L;
(3) soaking the soaked hydrogel in a reducing agent solution for 1-5h to obtain high-strength lignin/polyvinyl alcohol composite conductive hydrogel; the concentration of the reducing agent solution is 0.1-2 mol/L.
2. The high strength lignin/polyvinyl alcohol composite conductive hydrogel according to claim 1, wherein: the mass concentration of PVA in the composite hydrogel in the step (1) is 4.5-30%.
3. The high strength lignin/polyvinyl alcohol composite conductive hydrogel according to claim 1, wherein: the water soluble silver salt comprises silver nitrate.
4. The high strength lignin/polyvinyl alcohol composite conductive hydrogel according to claim 1, wherein: the reducing agent comprises at least one of sodium citrate, sodium borohydride, dopamine and ascorbic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910542444.0A CN110240774B (en) | 2019-06-21 | 2019-06-21 | High-strength lignin/polyvinyl alcohol composite conductive hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910542444.0A CN110240774B (en) | 2019-06-21 | 2019-06-21 | High-strength lignin/polyvinyl alcohol composite conductive hydrogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110240774A CN110240774A (en) | 2019-09-17 |
| CN110240774B true CN110240774B (en) | 2022-02-15 |
Family
ID=67888727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910542444.0A Active CN110240774B (en) | 2019-06-21 | 2019-06-21 | High-strength lignin/polyvinyl alcohol composite conductive hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110240774B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072780A (en) * | 2020-01-03 | 2021-07-06 | 中国石油天然气股份有限公司 | Antibacterial master batch, preparation method thereof and antibacterial ABS resin |
| CN111184975B (en) * | 2020-02-27 | 2021-07-02 | 中国科学院长春应用化学研究所 | Lignin type high-molecular hydrogel fire extinguishing agent and preparation method thereof |
| CN112480464B (en) * | 2020-11-19 | 2022-03-25 | 图们市华威友邦化工有限公司 | Hydrophobic lignin/cellulose aerogel oil-water separation material and preparation method and application thereof |
| KR102434379B1 (en) * | 2021-01-08 | 2022-08-19 | 인하대학교 산학협력단 | Esterified PVA-lignin Eco-friendly Resin, Fabrication Method Thereof and Eco-friendly Natural Fiber-reinforced Composite Comprising the Same |
| CN113004543B (en) * | 2021-02-26 | 2022-05-24 | 江南大学 | Nano lignin/polyvinyl alcohol composite medical hydrogel and preparation method thereof |
| CN113512209B (en) * | 2021-08-10 | 2022-04-15 | 吉林大学 | Preparation method of high-conductivity and high-sensitivity polyvinyl alcohol-based conductive hydrogel |
| CN113605094B (en) * | 2021-08-28 | 2023-04-28 | 苏州鱼得水电气科技有限公司 | Antibacterial degradable composite fiber and preparation method thereof |
| CN114736476B (en) * | 2022-03-27 | 2023-06-23 | 宁波大学 | Polyvinyl alcohol conductive microporous foaming material |
| CN115260530A (en) * | 2022-08-03 | 2022-11-01 | 华东理工大学 | Polyvinyl alcohol/lignin hydrogel with adjustable mechanical property and preparation method thereof |
| CN116462927B (en) * | 2023-05-17 | 2024-05-07 | 广州白云美湾产业发展有限公司 | Lignin sulfonic acid/polyvinyl alcohol composite film, preparation method thereof and application thereof in facial mask |
| CN116850135B (en) * | 2023-06-28 | 2024-07-30 | 广州白云美湾产业发展有限公司 | Antibacterial sodium lignin sulfonate/polyvinyl alcohol composite hydrogel and application thereof in preparation of cosmetics with acne removal effect |
| CN117045554B (en) * | 2023-08-18 | 2024-06-07 | 广州白云美湾产业发展有限公司 | TA@LS-Ag/PVA composite film, preparation method thereof and application thereof in preparing mask |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153438A (en) * | 2015-10-27 | 2015-12-16 | 南京林业大学 | Preparation method of high-strength high-swelling nanocellulose and polyving akohol composite hydrogel |
| CN106009442A (en) * | 2016-06-21 | 2016-10-12 | 天津大学 | Preparation method of nano-silver-loaded polyvinyl alcohol hydrogel |
| CN108948614A (en) * | 2018-07-18 | 2018-12-07 | 华南理工大学 | A kind of lignin/polyvinyl alcohol composite material and preparation method thereof |
-
2019
- 2019-06-21 CN CN201910542444.0A patent/CN110240774B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153438A (en) * | 2015-10-27 | 2015-12-16 | 南京林业大学 | Preparation method of high-strength high-swelling nanocellulose and polyving akohol composite hydrogel |
| CN106009442A (en) * | 2016-06-21 | 2016-10-12 | 天津大学 | Preparation method of nano-silver-loaded polyvinyl alcohol hydrogel |
| CN108948614A (en) * | 2018-07-18 | 2018-12-07 | 华南理工大学 | A kind of lignin/polyvinyl alcohol composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| In situ reduction of silver nanoparticles in the lignin based hydrogel forenhanced antibacterial application;Man Li 等;《Colloids and Surfaces B: Biointerfaces》;20190216;第370-376页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110240774A (en) | 2019-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110240774B (en) | High-strength lignin/polyvinyl alcohol composite conductive hydrogel and preparation method thereof | |
| CN109847661B (en) | Preparation method of graphene oxide and silver nanowire assembled ternary elastic hydrogel | |
| CN110922611B (en) | MXene hydrogel with high strength, conductivity and high and low temperature resistance as well as preparation method and application thereof | |
| CN112375235B (en) | Isotropic high-toughness organic hydrogel electrolyte and preparation method thereof | |
| CN108948614B (en) | Lignin/polyvinyl alcohol composite material and preparation method thereof | |
| CN110885476B (en) | Secondary doped graphene oxide/alkali-soluble chitosan-polyaniline-polyacrylamide composite conductive hydrogel prepared by one-pot method | |
| CN110627470B (en) | Double-network reinforced composite quick-drying gel cement material and preparation method thereof | |
| CN111763334B (en) | Preparation of double-network conductive hydrogel and application of double-network conductive hydrogel in strain sensor | |
| CN101445615B (en) | Soyabean protein/dialdehyde starch/nano silver composite membrane, preparation method and application thereof | |
| CN103087336A (en) | Preparation method of graphene oxide/konjac glucomannan degradable composite film material | |
| CN112521630A (en) | Preparation method and application of green flexible conductive anti-freezing hydrogel | |
| CN115806407B (en) | Calcium oxide filler for aerated brick and production process thereof | |
| CN111620617A (en) | Ultrahigh-performance cement-based composite material for sensor, sensor and preparation method | |
| CN111995770A (en) | Preparation method of physical combined network hydrogel | |
| CN111019159B (en) | Low-temperature hydrogel electrolyte and preparation method thereof | |
| Huang et al. | Lignin nanorods reinforced nanocomposite hydrogels with UV-shielding, anti-freezing and anti-drying applications | |
| CN109251451B (en) | Preparation method of pH-sensitive xanthan gum/polyvinyl alcohol hydrogel | |
| Zheng et al. | Lignocellulose hydrogels fabricated from corncob residues through a green solvent system | |
| CN117430904A (en) | Water-resistant conductive hydrogel with excellent comprehensive performance, and preparation method and application thereof | |
| CN113214657A (en) | High-strength, high-conductivity and flexible soybean protein film and preparation method thereof | |
| CN112210114A (en) | Preparation method of ultrahigh-strength multifunctional polyvinyl alcohol-based oil gel elastomer | |
| CN106905454A (en) | A kind of Graphene crystal composite polrvinyl chloride anti-biotic material and preparation method thereof | |
| Gu et al. | Plant‐based Biomass/Polyvinyl Alcohol Gels for Flexible Sensors | |
| CN115558152B (en) | Double-drying degradable nano-cellulose composite antibacterial aerogel and preparation method and application thereof | |
| CN114672044A (en) | Cellulose conductive hydrogel and preparation method 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 |