CN114656654A - Modified lignin self-repairing conductive hydrogel and preparation method and application thereof - Google Patents

Modified lignin self-repairing conductive hydrogel and preparation method and application thereof Download PDF

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CN114656654A
CN114656654A CN202210308184.2A CN202210308184A CN114656654A CN 114656654 A CN114656654 A CN 114656654A CN 202210308184 A CN202210308184 A CN 202210308184A CN 114656654 A CN114656654 A CN 114656654A
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lignin
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胡雅欣
董若羽
房静玲
陈朕楠
秦恒飞
罗世鹏
周月
杨洲
罗京
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Abstract

The invention relates to a modified lignin self-repairing conductive hydrogel and a preparation method and application thereof, and the specific preparation process comprises the steps of carrying out substitution reaction on hydroxyalkylated lignin and N-halogenated alkyl maleimide to obtain modified hydroxyalkyl lignin containing dienophile; then the hydroxyl on the N-hydroxyalkyl substituted polyacrylamide and the hydroxyl on the hydroxyalkyl lignin modified by the dienophile are subjected to coupling reaction under the action of carbonate or cyanate compound to obtain the grafted dienophile modified lignin; and finally, carrying out Diels-Alder reaction on the symmetric diene compound and the grafted dienophile modified lignin under the heating condition and generating crosslinking, thus obtaining the modified lignin self-repairing conductive hydrogel with hydrogen bonds and reversible covalent bonds. The conductive hydrogel can realize a self-repairing function within 10-15min, and has good mechanical tensile property and conductivity.

Description

Modified lignin self-repairing conductive hydrogel and preparation method and application thereof
Technical Field
The invention relates to the technical field of modified lignin, in particular to a self-repairing conductive hydrogel of modified lignin as well as a preparation method and application thereof.
Background
The hydrogel is a soft substance which is rich in water and has a three-dimensional network structure, can maintain a certain shape in water and is not dissolved by water, and also can show excellent water absorbability, water retentivity and gel stability, and can be used as a good matrix, carrier or framework of a functional material. The hydrogel is treated to a certain degree, and a conductive medium is introduced to prepare the hydrogel with a conductive function, so that the research hotspot in recent years is formed. The conductive hydrogel organically combines a hydrophilic matrix and a conductive medium, is a composite hydrogel with good processability, higher flexibility and excellent electrochemical performance, and is an ideal material for future flexible electronic devices.
The self-repairing material has the capabilities of self monitoring, self adaption and self healing, can successfully sense and repair external damage, and achieves the self-repairing function through the interaction of self composition. Self-repairing materials can be classified into intrinsic types and extrinsic types according to whether a repairing agent is added or not. The external-aid self-repairing material realizes a repairing effect by implanting microcapsules or hollow fibers and the like filled with a repairing agent into a polymer matrix. The intrinsic self-repairing material does not need to be additionally added with an embedding repairing agent, and realizes the self-repairing function of the material by utilizing the reversible dynamic chemical action or the supermolecule action in a molecular network or under certain external stimulation. The self-repairing function is realized based on the dynamic chemical action of reversible covalent bonds (such as Diels-Alder reaction, disulfide bond and the like) and reversible non-covalent bonds (hydrogen bond action, metal ligand interaction, ion interaction and the like) in a molecular network.
The two materials are organically combined to form the self-repairing conductive hydrogel material, however, the conventional conductive polymer materials such as polyaniline, polypyrrole, polythiophene and the like are usually hard and brittle, and the technical problem to be solved by the invention is how to design the hydrogel material with better mechanical properties and with the conductive or antistatic function and the self-repairing function.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified lignin self-repairing conductive hydrogel and a preparation method and application thereof. The modified lignin self-repairing conductive hydrogel polymer is designed and prepared by taking alkali lignin as a raw material based on multiple hydrogen bonds and reversible imine bonds, can realize a self-repairing function within 10-15min, and has good mechanical tensile property and conductivity (or antistatic function).
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of modified lignin self-repairing conductive hydrogel comprises the following steps:
Figure BDA0003566611460000021
(1) carrying out substitution reaction on the hydroxyalkylated lignin I and N-halogenated alkyl maleimide II to obtain modified hydroxyalkyl lignin III containing dienophile; wherein X in the N-halogenated alkyl maleimide II is halogen and R1Is an ester group;
Figure BDA0003566611460000022
(2) carrying out coupling reaction on hydroxyl on the hydroxyalkyl lignin III containing the dienophile modification and hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of carbonate or cyanate ester compound to obtain grafted dienophile modified lignin V; wherein N in the N-hydroxyalkyl substituted polyacrylamide IV represents polymerization degree and R2Is an alkyl group;
Figure BDA0003566611460000031
(3) carrying out Diels-Alder reaction on a symmetrical diene compound VI and the grafted dienophile modified lignin V under the heating condition and generating cross-linking, thus obtaining the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds;
wherein a in the symmetrical diene compound VI is a repeating unit, and the number of the repeating units is at least 2; y is one of nitrogen atom, oxygen atom and sulfur atom; r3Is an aromatic ring structure, R3And the other end of (b) and the other R in the repeating unit3And (4) connecting.
Further, R3In a manner including R3The linkage of the above bond, or the linkage of the repeating unit centered on a carbon atom, or the linkage of the repeating unit centered on a triazine ring.
Still further, the symmetrical diene compound VI in the step (3) has one of the following structural formulas:
Figure BDA0003566611460000032
y is one of nitrogen atom, oxygen atom and sulfur atom, and when Y is nitrogen atom, hydrogen atom or alkyl is connected with nitrogen atom. A pyridine group when Y is N, a furan group when Y is O, and a thiophene group when Y is S. Specifically, the method comprises the following steps: linear may be 4,4 '-bis (2 "-furyl) biphenyl, 4' -bis (2" -pyridyl) biphenyl, 4 '-bis (2 "-alkylpyridyl) biphenyl, 4' -bis (2" -thienyl) biphenyl; the plane triangle may be: 2,4, 6-tris (4- (2 '-furyl) phenyl-1, 3, 5-triazine, 2,4, 6-tris (4- (2' -thienyl) phenyl-1, 3, 5-triazine, 2,4, 6-tris (4- (2 '-pyridyl) phenyl-1, 3, 5-triazine, 2,4, 6-tris (4- (2' -alkylpyridyl) phenyl-1, 3, 5-triazine; the tetrahedral type may be: tetrakis (4- (2 '-furyl) phenylmethane), tetrakis (4- (2' -thienyl) phenylmethane), tetrakis (4- (2 '-pyridyl) phenylmethane), tetrakis (4- (2' -alkylpyridyl) phenylmethane).
Further, in the N-halogenated alkyl maleimide II in the step (1), X is chlorine, and R is1Is one of methyl acetate group, ethyl acetate group and butyl acetate group;
the carbonate or cyanate ester compound in the step (2) comprises one of triphosgene, TDI, IPDI, MDI, HMDI, HDI and LDI; the polymerization degree of N in the N-hydroxyalkyl substituted polyacrylamide IV in the step (2) is 500-5000-2Is C1-C10Alkyl group of (1).
Further, in the step (1), the hydroxyalkylated lignin I is obtained by directly carrying out nucleophilic substitution on lignin serving as a raw material and an electrophilic reagent in a solvent-free system; the electrophilic reagent is one of ethylene carbonate, 1, 3-oxathiolane-2-ketone, 2-oxazolidone and derivatives thereof; the mass ratio of the lignin to the electrophilic reagent is 1 (6-10). Preferably, the hydroxyalkylated lignin i is hydroxyethyl lignin or hydroxypropyl lignin.
Further, the mass ratio of the hydroxyalkylated lignin I to the N-halogenated alkyl maleimide II in the step (1) is 1 (30-60), and the dosage is controlled so that the hydroxyl on the hydroxyalkylated lignin I does not completely participate in the substitution reaction; the mass ratio of the N-hydroxyalkyl substituted polyacrylamide IV, the modified hydroxyalkyl lignin III containing the dienophile and the carbonate or cyanate compound in the step (2) is (7-13) to 1 (2-4.5); in the step (3), the mass ratio of the symmetric diene compound VI to the grafted dienophile modified lignin V is 1 (10-20).
Further, the condition of the substitution reaction in the step (1) is that the reaction is carried out for 5 to 36 hours at a temperature of between 60 and 120 ℃; the coupling reaction in the step (2) is carried out under the condition of pH 4-7 and at the temperature of 30-50 ℃, and the reaction solvent is tetrahydrofuran; in the step (3), the temperature of the Diels-Alder reaction is 100-120 ℃, the reaction time is 2h, and the reaction solvent is benzene solvent.
On the other hand, the invention provides the modified lignin self-repairing conductive hydrogel prepared by the preparation method.
The last aspect of the invention provides application of the modified lignin self-repairing conductive hydrogel prepared by the preparation method in the fields of coatings, adhesives, wearable sensors or polymer electrolytes.
The beneficial technical effects are as follows: the method can obtain the modified lignin self-repairing conductive hydrogel with three-dimensional conjugated pi bonds-multiple hydrogen bonds-reversible covalent bonds; the method comprises the steps of firstly introducing maleimide groups into hydroxyalkylated lignin to replace part of hydroxyl groups in the hydroxyalkylated lignin, grafting the rest part of hydroxyl groups with hydroxyalkyl substituted polyacrylamide to form grafted modified lignin with hydrogen bonds, and then introducing a large conjugated system on the maleimide groups of the grafted modified lignin to form the modified lignin self-repairing conductive hydrogel with reversible covalent bonds, multiple hydrogen bonds and three-dimensional conjugated pi bonds with a conductive function, wherein the reversible covalent bonds have a good self-repairing function. The macromolecular polymer disclosed by the invention has better conductivity or antistatic property, better self-repairing function and mechanical property when being applied to the field of coatings, adhesives or wearable sensors, can realize the self-repairing healing function within 10-15min, and has better tensile property and conductivity.
Drawings
FIG. 1 is a route diagram of a self-repairing conductive hydrogel synthesis technology of modified lignin.
Fig. 2 is an SEM image of the modified lignin self-healing conductive hydrogel prepared in example 1, wherein a is 20 microns and b is 2 microns.
Fig. 3 is a cutting-self-healing graph of the modified lignin self-healing conductive hydrogel prepared in example 1, in which a is the complete conductive hydrogel, b is the cut conductive hydrogel, and c is the self-healing conductive hydrogel.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values.
Example 1
A preparation method of modified lignin self-repairing conductive hydrogel is shown in a synthesis technology roadmap in figure 1, and comprises the following steps:
(1) 6.6g of ethylene carbonate directly generates nucleophilic substitution with 1g of lignin under the solvent-free condition: reacting at 90 ℃ for 12h to quickly obtain hydroxyethyl lignin I in one step;
carrying out substitution reaction on 0.6g of hydroxyethyl lignin I and 35g of N- (chloroacetic acid-2-ethyl) maleimide II at 90 ℃ for 12h to obtain dienophile-containing modified hydroxyethyl lignin III;
(2) dissolving 4g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile initiator in 30mL of Tetrahydrofuran (THF) to perform free radical polymerization for 6h at 65 ℃ to form N-hydroxymethyl polyacrylamide IV, and measuring the polymerization degree N of the N-hydroxymethyl polyacrylamide IV to be 610;
3.5g N-hydroxymethyl polyacrylamide IV and 0.44g of the hydroxyethyl lignin III modified by the dienophile are subjected to coupling reaction of hydroxyl on the hydroxyethyl lignin III modified by the dienophile and hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17g of triphosgene (the reaction condition is that the coupling reaction is carried out in tetrahydrofuran at 40 ℃ under the condition that triethylamine is used for adjusting the neutral condition), so as to obtain grafted dienophile modified lignin V;
(3) 0.21g of a symmetrical diene compound VI (in particular 4,4 '-bis (2' -furanyl) biphenyl, chemical structure:
Figure BDA0003566611460000061
that is to say that in the compound VI Y is an oxygen atom and the number of the repeating units is 2, R3Is phenyl) and 4.2g of the graft-type dienophile-modified lignin v were subjected to Diels-Alder reaction (2h) at 110 ℃ and crosslinking was generated (other reaction conditions: toluene is adopted as a solvent), and the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds is prepared.
An SEM image of the modified lignin self-repairing conductive hydrogel vii prepared in this example is shown in fig. 2, and as can be seen from fig. 2, it has a microscopic three-dimensional network-like structure and a honeycomb-like pore structure.
Example 2
A preparation method of modified lignin self-repairing conductive hydrogel is shown in a synthesis technology roadmap in figure 1, and comprises the following steps:
(1) directly carrying out nucleophilic substitution on 7.2g of ethylene carbonate and 1g of lignin in the absence of a solvent under the following reaction conditions: reacting for 24 hours at 100 ℃, and quickly obtaining hydroxyethyl lignin I by one step;
carrying out substitution reaction on 0.6g of hydroxyethyl lignin I and 35g of N- (chloroacetic acid-3-propyl) maleimide II at 90 ℃ for 12h to obtain diene-modified hydroxyethyl lignin III;
(2) dissolving 4g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile initiator in 30mL of Tetrahydrofuran (THF) to perform free radical polymerization for 8h at 65 ℃ to form N-hydroxymethyl polyacrylamide IV, and measuring the polymerization degree N of the N-hydroxymethyl polyacrylamide IV to be 1050;
3.5g N-hydroxymethyl polyacrylamide IV and 0.39g of diene-containing modified hydroxyethyl lignin III are subjected to coupling reaction of hydroxyl on the diene-containing modified hydroxyethyl lignin III and hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17g of triphosgene (the reaction condition is that the coupling reaction is carried out in tetrahydrofuran at 30 ℃ under the condition that triethylamine is used for adjusting the neutral condition), so as to obtain grafted dienophile-modified lignin V;
(3) 0.21g of a symmetrical diene compound VI (specifically 4,4 '-bis (2' -furyl) biphenyl, chemical structure:
Figure BDA0003566611460000071
namely, in the compound VI, Y is an oxygen atom and the number of the repeating units is 2, R3Is phenyl) and 3.78g of the graft-type dienophile-modified lignin v were subjected to Diels-Alder reaction (2h) at 110 ℃ and cross-linking was generated (other reaction conditions: xylene is used as solvent), thus obtaining the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds.
The SEM microstructure of the modified lignin self-repairing conductive hydrogel VII prepared in the embodiment is the same as that of the product prepared in the embodiment 1, and the modified lignin self-repairing conductive hydrogel VII still has a microscopic three-dimensional network structure and a honeycomb pore structure.
Example 3
A preparation method of modified lignin self-repairing conductive hydrogel is shown in a synthesis technology roadmap in figure 1, and comprises the following steps:
(1) 7.6g of 1, 3-dioxan-2-one are directly nucleophilic substituted without solvent with 1g of lignin, the reaction conditions being: reacting at 110 ℃ for 10h to quickly obtain hydroxypropyl lignin I in one step;
carrying out substitution reaction on 0.6g of hydroxypropyl lignin I and 35g of N- (chloroacetic acid-4-butyl) maleimide II at 90 ℃ for 12h to obtain diene-containing modified hydroxypropyl lignin III;
(2) dissolving 4g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile initiator in 30mL of Tetrahydrofuran (THF) to perform free radical polymerization for 4h at 75 ℃ to form N-hydroxymethyl polyacrylamide IV, wherein the polymerization degree N of the IV is 830;
3.5g N-hydroxymethyl polyacrylamide IV and 0.35g of diene-containing modified hydroxypropyl lignin III are subjected to coupling reaction of hydroxyl on the diene-containing modified hydroxypropyl lignin III and hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17g of triphosgene (the reaction condition is that the coupling reaction is carried out in tetrahydrofuran at 50 ℃ under the condition that triethylamine is used for adjusting the neutral condition), so as to obtain grafted dienophile-modified lignin V;
(3) 0.21g of a symmetrical diene compound VI (in particular 4,4 '-bis (2' -furanyl) biphenyl, chemical structure:
Figure BDA0003566611460000072
namely, in the compound VI, Y is an oxygen atom and the number of the repeating units is 2, R3Is phenyl) and 3.36g of the grafted dienophile-modified lignin v were subjected to a Diels-Alder reaction (2h) at 110 ℃ and cross-linking was generated (other reaction conditions: benzene is adopted as a solvent), thus obtaining the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds.
The SEM microstructure of the modified lignin self-repairing conductive hydrogel VII prepared in the embodiment is the same as that of the product prepared in the embodiment 1, and the modified lignin self-repairing conductive hydrogel VII still has a microscopic three-dimensional network structure and a honeycomb-shaped pore structure.
Example 4
A preparation method of modified lignin self-repairing conductive hydrogel is shown in a synthesis technology roadmap in figure 1, and comprises the following steps:
(1) 7.6g of 1, 3-dioxane-2-one are directly nucleophilic substituted without solvent with 1g of lignin, the reaction conditions being: reacting at 80 ℃ for 30h to quickly obtain hydroxypropyl lignin I in one step;
carrying out substitution reaction on 0.6g of hydroxypropyl lignin I and 35g N- (chloroacetic acid-methylene) maleimide II at 90 ℃ for 12h to obtain diene-containing modified hydroxypropyl lignin III;
(2) dissolving 4g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile initiator in 30mL of Tetrahydrofuran (THF) to perform free radical polymerization for 6h at 65 ℃ to form N-hydroxymethyl polyacrylamide IV, and measuring the polymerization degree N of the N-hydroxymethyl polyacrylamide IV to be 620;
3.5g N-hydroxymethyl polyacrylamide IV and 0.33g of diene-containing modified hydroxypropyl lignin III are subjected to coupling reaction of hydroxyl on the diene-containing modified hydroxypropyl lignin III and hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17g of triphosgene (the reaction condition is that the coupling reaction is carried out in tetrahydrofuran at 40 ℃ under the condition that the pH is adjusted to be 5-6 by triethylamine), so as to obtain grafted dienophile modified lignin V;
(3) 0.21g of a symmetrical diene compound VI (specifically 4,4 '-bis (2' -furyl) biphenyl, chemical structure:
Figure BDA0003566611460000081
that is to say that in the compound VI Y is an oxygen atom and the number of the repeating units is 2, R3Is phenyl) and 2.94g of the graft-type dienophile-modified lignin v were subjected to Diels-Alder reaction (2h) at 110 ℃ and crosslinking was generated (other reaction conditions: benzene is adopted as a solvent), thus obtaining the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds.
The SEM microstructure of the modified lignin self-repairing conductive hydrogel VII prepared in the embodiment is the same as that of the product prepared in the embodiment 1, and the modified lignin self-repairing conductive hydrogel VII still has a microscopic three-dimensional network structure and a honeycomb pore structure.
Example 5
A preparation method of modified lignin self-repairing conductive hydrogel is shown in a synthesis technology roadmap in figure 1, and comprises the following steps:
(1) directly carrying out nucleophilic substitution on 8.2g of ethylene carbonate and 1g of lignin in the absence of a solvent, wherein the reaction conditions are as follows: reacting for 12 hours at 100 ℃, and quickly obtaining hydroxyethyl lignin I by one step;
performing substitution reaction on 0.6g of hydroxyethyl lignin I and 35g N- (ethyl chloroacetate) maleimide II at 90 ℃ for 12h to obtain diene-modified hydroxyalkyl lignin III;
(2) dissolving 4g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile initiator in 30mL of Tetrahydrofuran (THF) to perform free radical polymerization for 6h at 65 ℃ to form N-hydroxymethyl polyacrylamide IV, and measuring the polymerization degree N of the N-hydroxymethyl polyacrylamide IV to be 610;
3.5g N-hydroxymethyl polyacrylamide IV and 0.31g of diene-containing modified hydroxyethyl lignin III are subjected to coupling reaction of hydroxyl on the diene-containing modified hydroxyethyl lignin III and hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17g of triphosgene (the reaction condition is that coupling reaction is carried out in tetrahydrofuran at 40 ℃ under the condition that the pH is adjusted to be 5-6 by triethylamine), so as to obtain graft type dienophile modified lignin V;
(3) 0.21g of a symmetrical diene compound VI (in particular 4,4 '-bis (2' -thienyl) biphenyl, chemical structure:
Figure BDA0003566611460000091
namely, in the compound VI, Y is a sulfur atom, the number of the repeating units is 2, R3Is phenyl) and 2.52g of the graft-type dienophile-modified lignin v were subjected to Diels-Alder reaction (2h) at 110 ℃ and cross-linking was generated (other reaction conditions: xylene is used as solvent), thus obtaining the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds.
The SEM microstructure of the modified lignin self-repairing conductive hydrogel VII prepared in the embodiment is the same as that of the product prepared in the embodiment 1, and the modified lignin self-repairing conductive hydrogel VII still has a microscopic three-dimensional network structure and a honeycomb pore structure.
Example 6
A preparation method of modified lignin self-repairing conductive hydrogel is shown in a synthesis technology roadmap in figure 1, and comprises the following steps:
(1) directly carrying out nucleophilic substitution on 8.6g of ethylene carbonate and 1g of lignin in the absence of a solvent, wherein the reaction conditions are as follows: reacting for 12 hours at 90 ℃, and quickly obtaining hydroxyethyl lignin I in one step;
performing substitution reaction on 0.6g of hydroxyethyl lignin I and 35g N- (ethyl chloroacetate) maleimide II at 90 ℃ for 12h to obtain diene-modified hydroxyalkyl lignin III;
(2) dissolving 4g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile initiator in 30mL of Tetrahydrofuran (THF) to perform free radical polymerization for 6h at 65 ℃ to form N-hydroxymethyl polyacrylamide IV, and measuring the polymerization degree N of the N-hydroxymethyl polyacrylamide IV to be 620;
3.5g N-hydroxymethyl polyacrylamide IV and 0.29g of the hydroxyalkyl lignin III modified by the diene are subjected to coupling reaction of hydroxyl on the hydroxyalkyl lignin III modified by the diene and hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17g of triphosgene (the reaction condition is that the coupling reaction is carried out in tetrahydrofuran at 30 ℃ under the condition that the pH is adjusted to be 5-6 by triethylamine), so as to obtain graft dienophile modified lignin V;
(3) 0.21g of a symmetrical diene compound VI (specifically, 4 '-bis (2' -pyridyl) biphenyl, chemical structure:
Figure BDA0003566611460000092
namely, in the compound VI, Y is a nitrogen atom, the number of the repeating units is 2, R3Is phenyl) and 2.1g of the graft-type dienophile-modified lignin V are subjected to Diels-Alder reaction (2h) at the temperature of 110 ℃ and crosslinking is generated (other reaction conditions: benzene is adopted as a solvent), thus obtaining the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds.
The SEM microstructure of the modified lignin self-repairing conductive hydrogel VII prepared in the embodiment is the same as that of the product prepared in the embodiment 1, and the modified lignin self-repairing conductive hydrogel VII still has a microscopic three-dimensional network structure and a honeycomb-shaped pore structure.
Example 7
A preparation method of modified lignin self-repairing conductive hydrogel is shown in a synthesis technology roadmap in figure 1, and comprises the following steps:
(1) directly carrying out nucleophilic substitution on 7.6g of ethylene carbonate and 1g of lignin in the absence of a solvent under the following reaction conditions: reacting at 90 ℃ for 12h to quickly obtain hydroxyethyl lignin I in one step;
carrying out substitution reaction on 0.6g of hydroxyalkylated lignin I and 35g N- (ethyl chloroacetate) maleimide II at 90 ℃ for 12h to obtain dialkylated lignin III containing diene modification;
(2) dissolving 4g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile initiator in 30mL of Tetrahydrofuran (THF) to perform free radical polymerization for 8h at 75 ℃ to form N-hydroxymethyl polyacrylamide IV, and measuring the polymerization degree N of the N-hydroxymethyl polyacrylamide IV to be 1030;
3.5g N-hydroxymethyl polyacrylamide IV and 0.35g of the hydroxyalkyl lignin III modified by the diene are subjected to coupling reaction of the hydroxyl on the hydroxyalkyl lignin III modified by the diene and the hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17g of triphosgene (the reaction condition is that the coupling reaction is carried out in tetrahydrofuran at 40 ℃ under the condition that triethylamine is used for adjusting the neutral condition), so as to obtain the grafted dienophile modified lignin V;
(3) 0.21g of symmetrical diene compound VI (specifically 2,4, 6-tri (4- (2' -furyl) phenyl-1, 3, 5-triazine, namely compound VI, Y is an oxygen atom, the number of the repeating units is 3, and the symmetrical R is connected by taking the triazine as the center3，R3Is phenyl) and 3.36g of the grafted dienophile-modified lignin V are subjected to Diels-Alder reaction (2h) at the temperature of 110 ℃ and crosslinking is generated (other reaction conditions: xylene is used as solvent), thus obtaining the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds.
Example 8
A preparation method of modified lignin self-repairing conductive hydrogel is shown in a synthesis technology roadmap in figure 1, and comprises the following steps:
(1) directly carrying out nucleophilic substitution on 7.6g of ethylene carbonate and 1g of lignin in the absence of a solvent under the following reaction conditions: reacting at 90 ℃ for 12h to quickly obtain hydroxyethyl lignin I in one step;
performing substitution reaction on 0.6g of hydroxyethyl lignin I and 35g N- (ethyl chloroacetate) maleimide II at 90 ℃ for 12h to obtain diene-containing modified hydroxyethyl lignin III;
(2) dissolving 4g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile initiator in 30mL of Tetrahydrofuran (THF) to perform free radical polymerization for 6h at 65 ℃ to form N-hydroxymethyl polyacrylamide IV, and measuring the polymerization degree N of the N-hydroxymethyl polyacrylamide IV to be 620;
subjecting 3.5g N-hydroxymethyl polyacrylamide IV and 0.35g of diene-containing modified hydroxyethyl lignin III to coupling reaction of hydroxyl on the diene-containing modified hydroxyethyl lignin III and hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17g of triphosgene (the reaction condition is that coupling reaction is carried out in tetrahydrofuran at 40 ℃ under the condition that triethylamine is used for regulating neutral condition), thus obtaining graft dienophile modified lignin V;
(3) 0.21g of symmetrical diene compound VI (specifically, tetra (4- (2' -furyl) phenylmethane), namely the compound VI, wherein Y is an oxygen atom, the number of repeating units is 4, and the symmetrical connection R is centered on a carbon atom3，R3Phenyl) and 3.36g of the grafted dienophile modified lignin V are subjected to Diels-Alder reaction (2h) at the temperature of 110 ℃ and generate crosslinking ((other reaction conditions: toluene is adopted as a solvent), and the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds is prepared.
The SEM microstructure of the modified lignin self-repairing conductive hydrogel VII prepared in the embodiment is the same as that of the product prepared in the embodiment 1, and the modified lignin self-repairing conductive hydrogel VII still has a microscopic three-dimensional network structure and a honeycomb-shaped pore structure.
The product of the above example was coated between two wood boards, then hot-pressed at 110 ℃ and 1.0MPa for 10min, and the compacted composite wood boards were immersed in water at 80 ℃ for 2h, and then the bonding strength after immersion in hot water was measured and recorded as T1. Splicing the fracture samples which are subjected to hot water immersion and then are tested for bonding strength, hot-pressing and self-repairing for 10min at 110 ℃ and 1.0MPa, soaking the compacted composite wood board in water at 80 ℃ for 2h, and then measuring the bonding strength after the self-repairing is immersed in hot water and marking as T2. The self-repairing rate is a percentage value of T2 and T1. The self-healing process is shown in fig. 3. Specific performance data are shown in table 1.
TABLE 1 Properties of the modified Lignin self-healing conductive hydrogels prepared in the examples
T1(MPa) T2(MPa) Self repair Rate (%) Conductivity (S/m)
Example 1 1.28 1.18 92.2 7.9
Example 2 1.33 1.23 92.5 8.7
Example 3 1.39 1.30 93.5 8.6
Example 4 1.35 1.24 91.9 7.3
Example 5 1.31 1.20 91.6 9.1
Example 6 1.26 1.14 90.5 7.0
Example 7 1.37 1.28 93.4 9.6
Example 8 1.35 1.26 93.3 10.5
As can be seen from Table 1, the modified lignin conductive hydrogel disclosed by the invention has 90% of self-repairing healing performance, and is relatively good in conductivity, and the conductivity is more than 7S/m; in addition, the mechanical property is better, the self-repairing healed steel still has the tensile strength of more than 1.1MPa, and the elongation at break can still reach more than 700%.
The modified lignin self-repairing conductive hydrogel can be used as an adhesive to be applied to bonding of substances of various materials, wherein the substances of various materials comprise wood, metal, plastic, electronic devices and the like, and the modified lignin self-repairing conductive hydrogel has high bonding strength, good self-repairing performance and conductive or antistatic performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.

Claims (9)

1. A preparation method of modified lignin self-repairing conductive hydrogel is characterized by comprising the following steps:
Figure FDA0003566611450000011
(1) carrying out substitution reaction on the hydroxyalkylated lignin I and N-halogenated alkyl maleimide II to obtain modified hydroxyalkyl lignin III containing dienophile; wherein X in the N-halogenated alkyl maleimide II is halogen and R1Is an ester group;
Figure FDA0003566611450000012
(2) carrying out coupling reaction on hydroxyl on the hydroxyalkyl lignin III containing the modification of the dienophile and hydroxyl on the hydroxyalkyl lignin IV containing the modification of the dienophile under the action of a carbonate or cyanate compound to obtain grafted dienophile-modified lignin V; wherein N in the N-hydroxyalkyl substituted polyacrylamide IV represents polymerization degree and R2Is an alkyl group;
Figure FDA0003566611450000021
(3) carrying out Diels-Alder reaction on a symmetric diene compound VI and the grafted dienophile modified lignin V under the heating condition and generating cross-linking, thus preparing the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds;
wherein a in the symmetrical diene compound VI is a repeating unit, and the number of the repeating units is at least 2; y is one of nitrogen atom, oxygen atom and sulfur atom; r3Is an aromatic ring structure, R3And the other end of (b) and the other R in the repeating unit3And (4) connecting.
2. The preparation method of the modified lignin self-repairing conductive hydrogel according to claim 1, wherein R is R3In a manner including R3The linkage of the above bond, or the linkage of the repeating unit centered on a carbon atom, or the linkage of the repeating unit centered on a triazine ring.
3. The preparation method of the modified lignin self-repairing conductive hydrogel according to claim 2, wherein in the step (3), the symmetric diene compound VI has one of the following structural formulas:
Figure FDA0003566611450000022
y is one of nitrogen atom, oxygen atom and sulfur atom, and when Y is nitrogen atom, hydrogen atom or alkyl is connected with nitrogen atom.
4. The preparation method of the modified lignin self-repairing conductive hydrogel according to any one of claims 1 to 3, wherein in the N-haloalkylmaleimide II in the step (1), X is chlorine, R is chlorine1Is one of methyl acetate group, ethyl acetate group and butyl acetate group;
the carbonate or cyanate ester compound in the step (2)The substance comprises one of triphosgene, TDI, IPDI, MDI, HMDI, HDI and LDI; the polymerization degree of N in the N-hydroxyalkyl substituted polyacrylamide IV in the step (2) is 500-5000, R2Is C1-C10Alkyl group of (1).
5. The method for preparing the modified lignin self-repairing conductive hydrogel according to any one of claims 1 to 3, wherein the hydroxyalkylated lignin I in the step (1) is obtained by directly carrying out nucleophilic substitution on lignin serving as a raw material and an electrophilic reagent in a solvent-free system; the electrophilic reagent is one of ethylene carbonate, 1, 3-oxathiolane-2-ketone, 2-oxazolidinone and derivatives thereof; the mass ratio of the lignin to the electrophilic reagent is 1 (6-10).
6. The preparation method of the modified lignin self-repairing conductive hydrogel according to any one of claims 1 to 3, wherein the mass ratio of the hydroxyalkylated lignin I to the N-haloalkylmaleimide II in the step (1) is 1 (30-60), the hydroxyalkylated lignin I is hydroxyethyl lignin or hydroxypropyl lignin; the mass ratio of the N-hydroxyalkyl substituted polyacrylamide IV, the modified hydroxyalkyl lignin III containing the dienophile and the carbonate or cyanate compound in the step (2) is (7-13) to 1 (2-4.5); in the step (3), the mass ratio of the symmetric diene compound VI to the grafted dienophile modified lignin V is 1 (10-20).
7. The method for preparing the modified lignin self-repairing conductive hydrogel according to any one of claims 1 to 3, wherein the substitution reaction in step (1) is carried out at 60-120 ℃ for 5-18 h; the coupling reaction in the step (2) is carried out under the condition of pH 4-7 and at the temperature of 30-50 ℃, and the reaction solvent is tetrahydrofuran; in the step (3), the temperature of the Diels-Alder reaction is 100-120 ℃, the reaction time is 2h, and the reaction solvent is benzene solvent.
8. The modified lignin self-repairing conductive hydrogel prepared by the preparation method of any one of claims 1 to 6.
9. The application of the modified lignin self-repairing conductive hydrogel prepared by the preparation method of any one of claims 1 to 6 in the fields of coatings, adhesives, wearable sensors or polymer electrolytes.
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