CN114656654B - 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 PDFInfo
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Abstract
The invention relates to a modified lignin self-repairing conductive hydrogel and a preparation method and application thereof, wherein the specific preparation process comprises the steps of firstly carrying out substitution reaction on hydroxyalkylated lignin and N-halogenated alkyl maleimide to obtain modified hydroxyalkyllignin 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 a coupling reaction under the action of a carbonic ester or cyanate ester compound to obtain grafted dienophile modified lignin; and finally, carrying out Diels-Alder reaction on the symmetrical diene compound and grafted dienophile modified lignin under the heating condition and generating crosslinking to obtain 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
Technical Field
The invention relates to the technical field of modified lignin, in particular to a modified lignin self-repairing conductive hydrogel and a preparation method and application thereof.
Background
The hydrogel is a soft substance which contains abundant water and has a three-dimensional network structure, can maintain a certain shape in water, is not dissolved by water, can also show excellent water absorption, water retention and gel stability, and can be used as a good matrix, carrier or skeleton of a functional material. The hydrogel is treated to a certain extent, and the conductive medium is introduced to prepare the hydrogel with a conductive function, so that the hydrogel becomes a research hot spot in recent years. 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 flexible electronic devices in the future.
The self-repairing material has self-monitoring, self-adapting and self-healing capabilities, can successfully sense and repair external damage, and achieves a self-repairing function through self-composition interaction. Self-healing materials can be classified into two main types, intrinsic and extrinsic, depending on whether a healing agent is added. The external-assistance self-repairing material realizes the repairing effect by implanting microcapsules or hollow fibers and the like filled with the repairing agent into a polymer matrix. The intrinsic self-repairing material does not need to additionally add an embedding repairing agent, and the self-repairing function of the material is realized by utilizing reversible dynamic chemical action or supermolecular action in a molecular network spontaneously or under certain external stimulus. The self-healing function is realized based on dynamic chemical actions of reversible covalent bonds (such as Diels-Alder reaction, disulfide bond, etc.) and reversible non-covalent bonds (hydrogen bonding action, metal ligand interaction, ion interaction, etc.) in a molecular network.
The self-repairing conductive hydrogel material is formed by organically combining the conductive polymer materials, such as polyaniline, polypyrrole, polythiophene and the like, which are commonly used at present, are hard and brittle, and how to design the hydrogel material with good mechanical properties, conductive or antistatic function and self-repairing function is the technical problem to be solved by the invention.
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. According to the invention, the alkali lignin is used as a raw material, and the modified lignin self-repairing conductive hydrogel polymer is designed and prepared based on multiple hydrogen bonds and reversible imine bonds, so that the modified lignin self-repairing conductive hydrogel 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 above purpose, the invention is realized by the following technical scheme:
a preparation method of modified lignin self-repairing conductive hydrogel comprises the following steps:
(1) Carrying out substitution reaction on hydroxyalkylated lignin I and N-halogenated alkyl maleimide II to obtain hydroxyalkylated lignin III containing dienophile modification; wherein X in the N-halogenated alkyl maleimide II is halogen or R 1 Is an ester group;
(2) The coupling reaction of the hydroxyl on the modified hydroxyalkyl lignin III containing dienophile and the hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV is carried out under the action of carbonic ester or cyanate ester compound to obtain grafted dienophile modified lignin V; wherein N in the N-hydroxyalkyl substituted polyacrylamide IV represents the polymerization degree and R 2 Is an alkylene group;
(3) The symmetrical diene compound VI and the grafted dienophile modified lignin V are subjected to Diels-Alder reaction under the heating condition and are crosslinked, so that the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds is prepared;
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; r is R 3 Is of aromatic ring structure, R 3 And the other end of the repeating unit is R 3 And (5) connection.
Further, R 3 The connection mode of (C) comprises R 3 The bond is a bond to the repeating unit around a carbon atom, or a bond to the repeating unit around a triazine ring.
Still further, the symmetrical diene compound vi in step (3) has one of the following structural formulas:
y is one of nitrogen atom, oxygen atom and sulfur atom, and when Y is nitrogen atom, the connection with the nitrogen atom is hydrogen atom or alkyl. Y is an pyrrole group when N, a furan group when O, and a thiophene group when S. Specifically: the linear type can be 4,4' -bis (2-furyl) biphenyl, 4' -bis (2-pyrrolyl) biphenyl and 4,4' -bis (2-thienyl) biphenyl; the planar 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-pyrrolyl) phenyl-1, 3, 5-triazine, and the tetrahedral type may be tetrakis (4- (2-furyl) phenyl methane), tetrakis (4- (2-thienyl) phenyl methane), or tetrakis (4- (2-pyrrolyl) phenyl methane).
Further, the N in the step (1)-halogenated alkyl maleimide II wherein X is chlorine and R 1 Is one of methyl acetate group, ethyl acetate group and butyl acetate group;
the carbonate or cyanate ester compound in step (2) comprises one of triphosgene, TDI, IPDI, MDI, HMDI, HDI, LDI; the polymerization degree of N in the N-hydroxyalkyl substituted polyacrylamide IV in the step (2) is 500-5000 and R 2 Is C 1 -C 10 Alkylene groups of (a).
Further, the step (1) is characterized in that the hydroxyalkylated lignin I is obtained by taking lignin as a raw material and directly carrying out nucleophilic substitution with an electrophile under a solvent-free system; the electrophile is one of ethylene carbonate, 1, 3-oxathiolan-2-ketone and 2-oxazolidinone and derivatives thereof; the mass ratio of the lignin to the electrophile is 1 (6-10). Preferably, the hydroxyalkylated lignin I is hydroxyethyl lignin or hydroxypropyl lignin.
Further, in the step (1), the mass ratio of the hydroxyalkylated lignin I to the N-halogenated alkyl maleimide II is 1 (30-60), and the dosage is controlled so that the hydroxyl group on the hydroxyalkylated lignin I does not completely participate in the substitution reaction; in the step (2), the mass ratio of the N-hydroxyalkyl substituted polyacrylamide IV to the dienophile modified hydroxyalkyl lignin III to the carbonate or cyanate ester compound is (7-13) 1 (2-4.5); the mass ratio of the symmetrical diene compound VI to the grafted dienophile modified lignin V in the step (3) is 1 (10-20).
Further, the substitution reaction conditions in the step (1) are that the reaction is carried out at 60-120 ℃ for 5-36 hours; the condition of the coupling reaction in the step (2) is that the coupling reaction is carried out at the temperature of 30-50 ℃ under the condition that the pH=4-7, and the reaction solvent is tetrahydrofuran; the temperature of the Diels-Alder reaction in the step (3) is 100-120 ℃, the reaction time is 2h, and the reaction solvent is benzene solvent.
The invention also provides the modified lignin self-repairing conductive hydrogel prepared by the preparation method.
The invention also provides an application of the modified lignin self-repairing conductive hydrogel prepared by the preparation method in the fields of paint, 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 bond-multiple hydrogen bond-reversible covalent bond; according to the invention, maleimide groups are introduced into hydroxyalkylated lignin to replace part of hydroxyl groups, the rest of hydroxyl groups are used for grafting hydroxyalkyl to replace polyacrylamide to form grafted modified lignin with hydrogen bonds, and then a large conjugated system is introduced onto the maleimide groups of the grafted modified lignin, so that the modified lignin self-repairing conductive hydrogel with reversible covalent bonds, multiple hydrogen bonds and three-dimensional conjugated pi bonds with good self-repairing function is formed. The macromolecular polymer provided by the invention is applied to the fields of paint, adhesives or wearable sensors, has good conductivity or antistatic property, good self-repairing function and mechanical property, can realize self-repairing healing function within 10-15min, and has good tensile property and conductivity.
Drawings
FIG. 1 is a schematic diagram of a modified lignin self-repairing conductive hydrogel synthesis technology according to the present invention.
Fig. 2 is an SEM image of the modified lignin self-healing conductive hydrogel prepared in example 1, wherein a is 20 microns on scale and b is 2 microns on scale.
Fig. 3 is a cut-off-self-healing graph of the modified lignin self-healing conductive hydrogel prepared in example 1, wherein a is a complete conductive hydrogel, b is a cut conductive hydrogel, and c is a self-healing conductive hydrogel.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
Examples
A preparation method of modified lignin self-repairing conductive hydrogel, a synthetic technology route diagram is shown in figure 1, comprises the following steps:
(1) Directly nucleophilic substitution of 6.6 g ethylene carbonate with 1 g lignin under the condition of no solvent: reacting for 12 hours at 90 ℃ to quickly obtain the hydroxyethyl lignin I in one step;
substitution reaction is carried out on 0.6 g hydroxyethyl lignin I and 35 g of N- (chloroacetic acid-2-ethyl) maleimide II at 90 ℃ for 12h to obtain hydroxyethyl lignin III containing dienophile modification;
(2) Dissolving 4 g hydroxymethyl acrylamide and 0.5 g azodiisobutyronitrile initiator in 30 mL Tetrahydrofuran (THF) to perform free radical polymerization at 65 ℃ for 6h to form N-hydroxymethyl polyacrylamide IV, wherein the polymerization degree N of the N-hydroxymethyl polyacrylamide IV is 610;
3.5 g of N-methylol polyacrylamide IV and 0.44 g of the modified hydroxyethyl lignin III containing dienophile are subjected to a coupling reaction (under the reaction condition that triethylamine is used for adjusting neutral condition, the coupling reaction is carried out in tetrahydrofuran at 40 ℃ C.) under the action of 1.17 g triphosgene, so as to obtain grafted dienophile modified lignin V;
(3) The symmetrical dienoic compound VI of 0.21. 0.21 g (in particular4,4' -bis (2-furyl) biphenyl, chemical structure:
that is, in the compound VI, Y is an oxygen atom, and the number of repeating units is 2, R 3 Phenyl) with 4.2. 4.2 g said grafted dienophile modified lignin v undergoes Diels-Alder reaction (2 h) at 110 ℃ and cross-links (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 image of the modified lignin self-repairing conductive hydrogel VII prepared in the embodiment is shown in fig. 2, and as can be seen from fig. 2, the modified lignin self-repairing conductive hydrogel VII has a microscopic three-dimensional network structure and a honeycomb pore structure.
Examples
A preparation method of modified lignin self-repairing conductive hydrogel, a synthetic technology route diagram is shown in figure 1, comprises the following steps:
(1) Directly nucleophilic substitution of 7.2 g ethylene carbonate with 1 g lignin in the absence of solvent, and the reaction conditions are as follows: reacting for 24 hours at 100 ℃ to quickly obtain the hydroxyethyl lignin I in one step;
substitution reaction is carried out on 0.6 g hydroxyethyl lignin I and 35 g of N- (chloroacetic acid-3-propyl) maleimide II at 90 ℃ for 12h to obtain hydroxyethyl lignin III containing diene modification;
(2) Dissolving 4 g hydroxymethyl acrylamide and 0.5 g azodiisobutyronitrile initiator in 30 mL Tetrahydrofuran (THF) to perform free radical polymerization at 65 ℃ for 8 h to form N-hydroxymethyl polyacrylamide IV, wherein the polymerization degree N of the N-hydroxymethyl polyacrylamide IV is 1050;
3.5 g of N-methylol polyacrylamide IV and 0.39 g of bis-alkene-containing modified hydroxyethyl lignin III are subjected to a coupling reaction under the action of 1.17 g triphosgene, wherein the coupling reaction of the hydroxyl group on the bis-alkene-containing modified hydroxyethyl lignin III and the hydroxyl group on the N-hydroxyalkyl-substituted polyacrylamide IV is carried out (the reaction condition is that triethylamine is used for adjusting the neutral condition, and the coupling reaction is carried out in tetrahydrofuran at 30 ℃ to obtain grafted dienophile modified lignin V;
(3) 0.21 g symmetrical diene compound VI (in particular, 4' -bis (2-furyl) biphenyl) has the chemical structure:
that is, in the compound VI, Y is an oxygen atom, and the number of repeating units is 2, R 3 Phenyl) with 3.78 g said grafted dienophile modified lignin v undergoes Diels-Alder reaction (2 h) at 110 ℃ and cross-links (other reaction conditions: and xylene is used as a solvent) to prepare 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 this example is the same as the product of example 1, and still has a microscopic three-dimensional network structure and a cellular pore structure.
Examples
A preparation method of modified lignin self-repairing conductive hydrogel, a synthetic technology route diagram is shown in figure 1, comprises the following steps:
(1) 7.6 g of 1, 3-dioxane-2-one is directly subjected to nucleophilic substitution with 1 g lignin in the absence of a solvent, and the reaction conditions are as follows: reacting at 110 ℃ for 10 h to quickly obtain hydroxypropyl lignin I in one step;
substitution reaction is carried out on 0.6 g hydroxypropyl lignin I and 35 g N- (chloroacetic acid-4-butyl) maleimide II at 90 ℃ for 12h to obtain modified hydroxypropyl lignin III containing diene;
(2) Dissolving 4 g methylol acrylamide and 0.5 g azodiisobutyronitrile initiator in 30 mL Tetrahydrofuran (THF) to perform free radical polymerization at 75 ℃ for 4h to form N-methylol polyacrylamide IV with a polymerization degree N of 830;
3.5 g of N-methylol polyacrylamide IV and 0.35 g of diene-containing modified hydroxypropyl lignin III are subjected to a coupling reaction (reaction conditions are that triethylamine is used for adjusting neutral conditions and coupling reaction is carried out in tetrahydrofuran at 50 ℃ under the action of 1.17 g triphosgene) on the diene-containing modified hydroxypropyl lignin III and the hydroxyl on the N-hydroxyalkyl-substituted polyacrylamide IV to obtain grafted dienophile modified lignin V;
(3) 0.21 g symmetrical diene compound VI (in particular, 4' -bis (2-furyl) biphenyl) has the chemical structure:
that is, in the compound VI, Y is an oxygen atom, and the number of repeating units is 2, R 3 Phenyl) with 3.36 g said grafted dienophile modified lignin v undergoes Diels-Alder reaction (2 h) at 110 ℃ and cross-links (other reaction conditions: benzene is used as solvent) to prepare 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 this example is the same as the product of example 1, and still has a microscopic three-dimensional network structure and a cellular pore structure.
Examples
A preparation method of modified lignin self-repairing conductive hydrogel, a synthetic technology route diagram is shown in figure 1, comprises the following steps:
(1) 7.6 g of 1, 3-dioxane-2-one is directly subjected to nucleophilic substitution with 1 g lignin in the absence of a solvent, and the reaction conditions are as follows: reacting for 30 hours at 80 ℃ to quickly obtain hydroxypropyl lignin I in one step;
substitution reaction of 0.6 g hydroxypropyl lignin I and 35 g N- (chloroacetic acid-methylene) maleimide II at 90 ℃ is carried out for 12h to obtain diallyl lignin III containing diene modification;
(2) Dissolving 4 g hydroxymethyl acrylamide and 0.5 g azodiisobutyronitrile initiator in 30 mL Tetrahydrofuran (THF) to perform free radical polymerization at 65 ℃ for 6h to form N-hydroxymethyl polyacrylamide IV, wherein the polymerization degree N of the N-hydroxymethyl polyacrylamide IV is measured to be 620;
3.5 g of N-methylol polyacrylamide IV and 0.33 g of diene-containing modified hydroxypropyl lignin III are subjected to a coupling reaction under the action of 1.17 g triphosgene, wherein the coupling reaction of the hydroxyl group on the diene-containing modified hydroxypropyl lignin III and the hydroxyl group on the N-hydroxyalkyl-substituted polyacrylamide IV is carried out (the reaction condition is that triethylamine is used for adjusting pH=5-6, and the coupling reaction is carried out in tetrahydrofuran at 40 ℃ to obtain grafted dienophile modified lignin V;
(3) 0.21 g symmetrical diene compound VI (in particular, 4' -bis (2-furyl) biphenyl) has the chemical structure:
that is, in the compound VI, Y is an oxygen atom, and the number of repeating units is 2, R 3 Phenyl) with 2.94 g said grafted dienophile modified lignin v undergoes Diels-Alder reaction (2 h) at 110 ℃ and cross-links (other reaction conditions: benzene is used as solvent) to prepare 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 this example is the same as the product of example 1, and still has a microscopic three-dimensional network structure and a cellular pore structure.
Examples
A preparation method of modified lignin self-repairing conductive hydrogel, a synthetic technology route diagram is shown in figure 1, comprises the following steps:
(1) Directly nucleophilic substitution of 8.2 g ethylene carbonate with 1 g lignin under the condition of no solvent: reacting for 12 hours at 100 ℃ to quickly obtain the hydroxyethyl lignin I in one step;
substitution reaction of 0.6 g hydroxyethyl lignin I and 35 g of N- (ethyl chloroacetate) maleimide II at 90 ℃ is carried out for 12h to obtain hydroxyalkyl lignin III containing diene modification;
(2) Dissolving 4 g hydroxymethyl acrylamide and 0.5 g azodiisobutyronitrile initiator in 30 mL Tetrahydrofuran (THF) to perform free radical polymerization at 65 ℃ for 6h to form N-hydroxymethyl polyacrylamide IV, wherein the polymerization degree N of the N-hydroxymethyl polyacrylamide IV is 610;
3.5 g of N-methylol polyacrylamide IV and 0.31 g of the diene-containing modified hydroxyethyl lignin III are subjected to a coupling reaction under the action of 1.17 g triphosgene, wherein the coupling reaction of the hydroxyl group on the diene-containing modified hydroxyethyl lignin III and the hydroxyl group on the N-hydroxyalkyl-substituted polyacrylamide IV is carried out (the reaction condition is that triethylamine is used for adjusting pH=5-6, and the coupling reaction is carried out in tetrahydrofuran at 40 ℃ to obtain grafted dienophile modified lignin V;
(3) 0.21 g symmetrical diene compound VI (in particular, 4' -bis (2-thienyl) biphenyl) has the chemical structure:
that is, in the compound VI, Y is a sulfur atom, and the number of repeating units is 2, R 3 Phenyl) with 2.52 g said grafted dienophile modified lignin v undergoes Diels-Alder reaction (2 h) at 110 ℃ and cross-links (other reaction conditions: and xylene is used as a solvent) to prepare 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 this example is the same as the product of example 1, and still has a microscopic three-dimensional network structure and a cellular pore structure.
Examples
A preparation method of modified lignin self-repairing conductive hydrogel, a synthetic technology route diagram is shown in figure 1, comprises the following steps:
(1) Directly nucleophilic substitution of 8.6 g ethylene carbonate with 1 g lignin under the condition of no solvent: reacting for 12 hours at 90 ℃ to quickly obtain the hydroxyethyl lignin I in one step;
substitution reaction of 0.6 g hydroxyethyl lignin I and 35 g of N- (ethyl chloroacetate) maleimide II at 90 ℃ is carried out for 12h to obtain hydroxyalkyl lignin III containing diene modification;
(2) Dissolving 4 g hydroxymethyl acrylamide and 0.5 g azodiisobutyronitrile initiator in 30 mL Tetrahydrofuran (THF) to perform free radical polymerization at 65 ℃ for 6h to form N-hydroxymethyl polyacrylamide IV, wherein the polymerization degree N of the N-hydroxymethyl polyacrylamide IV is measured to be 620;
3.5 g of N-methylol polyacrylamide IV and 0.29 g of the dialkylene modified hydroxyalkyl lignin III are subjected to a coupling reaction (under the reaction condition that triethylamine is used for adjusting pH=5-6 and the coupling reaction is carried out in tetrahydrofuran at 30 ℃ C.) under the action of 1.17 g triphosgene, so as to obtain grafted dienophile modified lignin V;
(3) 0.21 g symmetrical diene compound VI (in particular, 4' -bis (2-pyrrolyl) biphenyl) has the chemical structure:
that is, in the compound VI, Y is a nitrogen atom, and the repeating unit is 2, R 3 Phenyl) with 2.1 g said grafted dienophile modified lignin v undergoes Diels-Alder reaction (2 h) at 110 ℃ and cross-links (other reaction conditions: benzene is used as solvent) to prepare 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 this example is the same as the product of example 1, and still has a microscopic three-dimensional network structure and a cellular pore structure.
Examples
A preparation method of modified lignin self-repairing conductive hydrogel, a synthetic technology route diagram is shown in figure 1, comprises the following steps:
(1) Directly nucleophilic substitution of 7.6 g ethylene carbonate with 1 g lignin in the absence of solvent, and the reaction conditions are as follows: reacting for 12 hours at 90 ℃ to quickly obtain the hydroxyethyl lignin I in one step;
substitution reaction of 0.6 g hydroxyalkylated lignin I with 35 g N- (ethyl chloroacetate) maleimide II at 90deg.C for 12-h to obtain hydroxyalkyllignin III containing modification of diene;
(2) Dissolving 4 g hydroxymethyl acrylamide and 0.5 g azodiisobutyronitrile initiator in 30 mL Tetrahydrofuran (THF) to perform free radical polymerization at 75 ℃ for 8 h to form N-hydroxymethyl polyacrylamide IV, wherein the polymerization degree N of the N-hydroxymethyl polyacrylamide IV is 1030;
3.5 g of N-methylol polyacrylamide IV and 0.35 g of the dialkylene modified hydroxyalkyl lignin III are subjected to a coupling reaction (reaction conditions are that triethylamine is used for adjusting neutral conditions and the coupling reaction is carried out in tetrahydrofuran at 40 ℃ C.) on the hydroxyl group on the dialkylene modified hydroxyalkyl lignin III and the hydroxyl group on the N-hydroxyalkyl substituted polyacrylamide IV under the action of 1.17 g triphosgene to obtain grafted dienophile modified lignin V;
(3) 0.21 g symmetrical diene compound VI (in particular 2,4, 6-tris (4- (2-furyl) phenyl-1, 3, 5-triazine, i.e. compound VI in which Y is an oxygen atom and the repeating units are 3 and R is symmetrically connected with triazine as the center 3 ，R 3 Phenyl) with 3.36 g said grafted dienophile modified lignin v undergoes Diels-Alder reaction (2 h) at 110 ℃ and cross-links (other reaction conditions: and xylene is used as a solvent) to prepare the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds.
Examples
A preparation method of modified lignin self-repairing conductive hydrogel, a synthetic technology route diagram is shown in figure 1, comprises the following steps:
(1) Directly nucleophilic substitution of 7.6 g ethylene carbonate with 1 g lignin in the absence of solvent, and the reaction conditions are as follows: reacting for 12 hours at 90 ℃ to quickly obtain the hydroxyethyl lignin I in one step;
substitution reaction is carried out on 0.6 g hydroxyethyl lignin I and 35 g of N- (ethyl chloroacetate) maleimide II at 90 ℃ for 12h to obtain modified hydroxyethyl lignin III containing diene;
(2) Dissolving 4 g hydroxymethyl acrylamide and 0.5 g azodiisobutyronitrile initiator in 30 mL Tetrahydrofuran (THF) to perform free radical polymerization at 65 ℃ for 6h to form N-hydroxymethyl polyacrylamide IV, wherein the polymerization degree N of the N-hydroxymethyl polyacrylamide IV is measured to be 620;
3.5 g of N-methylol polyacrylamide IV and 0.35 g of the diene-containing modified hydroxyethyl lignin III are subjected to a coupling reaction (under the reaction condition that triethylamine is used for adjusting neutral conditions and the coupling reaction is carried out in tetrahydrofuran at 40 ℃ C.) under the action of 1.17 g triphosgene, so as to obtain grafted dienophile modified lignin V;
(3) The symmetrical diene compound VI of 0.21 g (specifically tetra (4- (2-furyl) phenyl methane), in which Y is oxygen atom, and the repeating unit is 4 and R is symmetrically connected with carbon atom as center 3 ，R 3 Phenyl) and 3.36 g of the grafted dienophile modified lignin V are subjected to Diels-Alder reaction (2 h) at 110 ℃ and cross-linking is generated ((other reaction conditions: toluene is adopted as a solvent), so that 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 this example is the same as the product of example 1, and still has a microscopic three-dimensional network structure and a cellular pore structure.
The product of the above example was covered between two wood boards, then hot-pressed at 110℃and 1.0MPa for 10min, and then the compacted composite wood board was immersed in water at 80℃for 2h, and then the bonding strength after immersing in hot water was measured and recorded as T1. And (3) re-splicing the broken samples with the bonding strength tested after hot water immersion, performing hot-pressing self-repairing at 110 ℃ and 1.0MPa for 10min, immersing the compacted composite wood board in water at 80 ℃ for 2h, and measuring the bonding strength after self-repairing hot water immersion and marking as T2. The self-repair rate is the percentage value of T2 to T1. The self-healing process is shown in figure 3. The specific performance data are shown in Table 1.
Table 1 Properties of the modified lignin self-healing conductive hydrogels prepared in examples
As shown in Table 1, the modified lignin conductive hydrogel has 90% of self-healing property, good conductivity and conductivity of above 7S/m; in addition, the mechanical property is better, the self-repairing and healing composite material still has tensile strength of more than 1.1MPa, and the elongation at break still can reach more than 700%.
The modified lignin self-repairing conductive hydrogel can be used as an adhesive for bonding substances of various materials, including wood, metal, plastic, electronic devices and the like, and has the advantages of high bonding strength, good self-repairing performance and conductive or antistatic performance.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The preparation method of the modified lignin self-repairing conductive hydrogel is characterized by comprising the following steps of:
(1) Carrying out substitution reaction on hydroxyalkylated lignin I and N-halogenated alkyl maleimide II to obtain hydroxyalkylated lignin III containing dienophile modification; wherein X in the N-halogenated alkyl maleimide II is halogen or R 1 Is an ester group;
(2) Coupling reaction between the hydroxyl on the modified hydroxyalkyl lignin III containing dienophile and the hydroxyl on the N-hydroxyalkyl substituted polyacrylamide IV is carried out by the N-hydroxyalkyl substituted polyacrylamide IV and the hydroxyalkyl lignin III containing dienophile modification under the action of a carbonate compound, so as to obtain grafted dienophile modified lignin V;
wherein N in the N-hydroxyalkyl substituted polyacrylamide IV represents the polymerization degree and R 2 Is an alkylene group;
the polymerization degree of N in the N-hydroxyalkyl substituted polyacrylamide IV is 500-5000;
(3) The symmetrical diene compound VI and the grafted dienophile modified lignin V are subjected to Diels-Alder reaction under the heating condition and are crosslinked, so that the modified lignin self-repairing conductive hydrogel VII with hydrogen bonds and reversible covalent bonds is prepared;
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; r is R 3 Is of aromatic ring structure, R 3 And the other end of the repeating unit is R 3 And (5) connection.
2. The method for preparing the modified lignin self-repairing conductive hydrogel according to claim 1, wherein R is as follows 3 The connection mode of (C) comprises R 3 The bond is a bond to the repeating unit around a carbon atom, or a bond to the repeating unit around a triazine ring.
3. The method for preparing a modified lignin self-repairing conductive hydrogel according to claim 2, wherein the symmetrical diene compound vi in the step (3) has one of the following structural formulas:
y is one of nitrogen atom, oxygen atom and sulfur atom, and when Y is nitrogen atom, the Y is pyrrole group.
4. A method for preparing a modified lignin self-healing conductive hydrogel according to any one of claims 1 to 3, wherein step (1)Wherein X in the N-halogenated alkyl maleimide II is chlorine, R 1 Is one of methyl acetate group, ethyl acetate group and butyl acetate group;
the carbonate compound in step (2) is triphosgene; r in step (2) 2 Is C 1 -C 10 Alkylene groups of (a).
5. A method for preparing a modified lignin self-repairing conductive hydrogel according to any one of claims 1 to 3, wherein the step (1) is characterized in that the hydroxyalkylated lignin i is obtained by directly nucleophilic substitution of lignin as a raw material with an electrophile in a solvent-free system; the electrophile is one of ethylene carbonate, 1, 3-oxathiolan-2-ketone and 2-oxazolidinone and derivatives thereof; the mass ratio of the lignin to the electrophile is 1 (6-10).
6. A method for preparing a modified lignin self-repairing conductive hydrogel according to any one of claims 1 to 3, wherein in step (1), the mass ratio of the hydroxyalkylated lignin i to the N-haloalkyl maleimide ii is 1 (30 to 60), and the hydroxyalkylated lignin i is hydroxyethyl lignin or hydroxypropyl lignin; in the step (2), the mass ratio of the N-hydroxyalkyl substituted polyacrylamide IV to the dienophile modified hydroxyalkyl lignin III to the carbonate compound is (7-13) 1 (2-4.5); the mass ratio of the symmetrical diene compound VI to the grafted dienophile modified lignin V in the step (3) is 1 (10-20).
7. A method of preparing a modified lignin self-healing conductive hydrogel according to any one of claims 1 to 3, wherein the substitution reaction conditions in step (1) are reaction 5 to 18 h at 60 to 120 ℃; the condition of the coupling reaction in the step (2) is that the coupling reaction is carried out at the temperature of 30-50 ℃ under the condition that the pH=4-7, and the reaction solvent is tetrahydrofuran; the temperature of the Diels-Alder reaction in the step (3) is 100-120 ℃, the reaction time is 2h, and the reaction solvent is benzene solvent.
8. A modified lignin self-healing conductive hydrogel made according to the method of any one of claims 1-6.
9. Use of the modified lignin self-healing conductive hydrogel prepared by the preparation method according to any one of claims 1-6 in the fields of paint, adhesives, wearable sensors or polymer electrolytes.
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| CN109517205A (en) * | 2018-09-29 | 2019-03-26 | 华南农业大学 | A kind of wooden hydrogel of dual network and the preparation method and application thereof |
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| CN109517205A (en) * | 2018-09-29 | 2019-03-26 | 华南农业大学 | A kind of wooden hydrogel of dual network and the preparation method and application thereof |
| CN111073325A (en) * | 2019-12-31 | 2020-04-28 | 华南理工大学 | Lignin/fiber thermoplastic composite material and preparation method thereof |
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