CN115305601B - Preparation method of high-strength high-toughness artificial spider silk based on double-crosslinked network - Google Patents
Preparation method of high-strength high-toughness artificial spider silk based on double-crosslinked network Download PDFInfo
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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- D01D5/06—Wet spinning methods
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- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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Abstract
The invention relates to a preparation method of high-strength high-toughness artificial spider silk based on a double-crosslinked network. The method uses cellulose nanocrystalline and polyrotaxane as cross-linking agents and prepares the fiber through wet spinning. The method comprises the following specific steps: 1) Polyvinyl alcohol is dissolved in dimethyl sulfoxide; 2) Respectively dispersing cellulose nanocrystals and polyrotaxane in a dimethyl sulfoxide solvent, and respectively reacting with excessive N, N-carbonyl diimidazole to generate intermediates; 3) Mixing the solutions and further reacting to obtain spinning solution, and respectively forming a rigid network structure with cellulose nanocrystals as crosslinking points and a slidable mechanical interlocking network structure with polyrotaxane as the crosslinking points; 4) Extruding the spinning solution into the coagulating liquid continuously and uniformly, and preparing the artificial spider silk by hot stretching, drying, curing and molding. The elongation at break exceeds 50%, the breaking strength exceeds 1GPa, and the toughness exceeds 350MJ/m 3 Has shape memory property. The invention can be applied to the fields of safety protection, flexible electronics, composite materials and the like.
Description
Technical Field
The invention relates to the technical field of chemical bionics, in particular to a preparation method of high-strength high-toughness artificial spider silk based on a double-crosslinked network.
Background
Natural spider silk has the characteristics of high tensile strength, large fracture strain, strong toughness and the like, so that the natural spider silk becomes one of the most widely used materials. The excellent mechanical properties of spider silk are derived from its own structure, its primary structure being amorphous regions crosslinked by β -sheet nanocrystals, providing strength and ductility to spider silk; and the energy dissipation in the stretching process is enhanced by the beta-chain secondary structure arranged in the beta-lamellar nanocrystalline in a stick-slip deformation mode. The natural spider silk can be used in the fields of wearable electronic products, artificial ligaments, artificial tendons, bulletproof vests and the like by utilizing the excellent mechanical properties and good biocompatibility of the natural spider silk. However, the yield of natural spider silk is far from meeting the demands of people, so that it is necessary to simulate the structure of natural spider silk and design artificial spider silk with similar performance to the natural spider silk.
Currently, some progress has been made in the field of artificial spider silk. The artificial spider silk produced by electrospinning can be mass-produced, but cannot be formed into individual fibers. The strength of the artificial spider silk obtained by simulating a natural spider silk structure and simultaneously simulating the spider silk protein with a primary structure and a secondary structure through dry spinning reaches 100Mpa. The breaking strength of the silk protein composite fiber prepared from the carbon nano tube and the silk protein reaches 600Mpa, and the breaking strain reaches 73%. The most widely studied artificial spider silk based on regenerated silk proteins, this method can obtain artificial spider silk having excellent mechanical properties. However, the artificial spider silks prepared by the methods have the problems of complex synthetic routes, inability of mass production and the like, and the large-scale application of the artificial spider silks in real-life production is greatly limited. Therefore, the development of the artificial spider silk which has excellent performance, simple preparation method and can be produced and prepared in large scale has great practical significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of high-strength high-toughness artificial spider silk based on a double-crosslinked network, and the obtained artificial spider silk has the properties of high strength, high toughness, high elongation, high modulus, shape memory and the like. The method takes polyvinyl alcohol, polyrotaxane and cellulose nanocrystals as raw materials, firstly uniformly dissolves the polyvinyl alcohol in dimethyl sulfoxide to form dispersion liquid, and then respectively overmuch N, N-carbonyl diimidazole is respectively added into the dimethyl sulfoxide dispersion liquid of the polyrotaxane and the cellulose nanocrystals to form two intermediates. And then mixing the dispersion solutions, and further carrying out a crosslinking reaction to obtain the composite spinning solution. And then obtaining the high-strength high-toughness artificial spider silk based on the double-crosslinked network through a wet spinning process and a heat treatment process. In this system, there is a rigid network with cellulose nanocrystals as cross-links, and a slidable mechanically interlocking network with polyrotaxane as cross-links. The elongation at break of the artificial spider silk is more than 60 percent, the breaking strength is more than 1GPa, and the toughness is more than 400MJ/m 3 The method comprises the steps of carrying out a first treatment on the surface of the And has a rapid shape memory function.
The specific technical scheme of the invention is as follows: the preparation method of the high-strength high-toughness artificial spider silk based on the double-crosslinked network comprises the following steps:
(1) Dissolving a polyvinyl alcohol matrix raw material into anhydrous dimethyl sulfoxide to form a uniform dispersion liquid, wherein the concentration is 5-20wt%;
(2) Dispersing cellulose nanocrystals in anhydrous dimethyl sulfoxide to form a uniform dispersion liquid, wherein the concentration is 0.1-3wt% of polyvinyl alcohol, and adding excessive N, N-carbonyl diimidazole to react with hydrophilic functional groups on the surface of the cellulose nanocrystals to form an intermediate;
(3) Dispersing polyrotaxane in anhydrous dimethyl sulfoxide to form uniform dispersion with the concentration of 0.1-10wt% of polyvinyl alcohol, and adding excessive N, N-carbonyl diimidazole to react with hydrophilic functional groups on the surface of cellulose nanocrystals to form an intermediate;
(4) Mixing the dispersibility, and further performing a crosslinking reaction to form a rigid network taking cellulose nanocrystals as crosslinking points and a slidable mechanical interlocking network taking polyrotaxane as the crosslinking points, thereby obtaining a composite spinning solution;
(5) Extruding the composite spinning solution through a spinning die head, solidifying through a poor solvent coagulating bath, and collecting by a roll shaft to form self-supporting nascent fibers; and (3) placing the nascent composite fiber in a baking oven at 180-220 ℃ for continuous thermal traction, wherein the stretching multiplying power is 2-12 times, and the heating time is 2-10 minutes, so as to obtain the final artificial spider silk fiber.
The average molecular weight of the polyvinyl alcohol matrix in the step (1) is 200,000, and the dissolution temperature is 80 ℃.
The polyvinyl alcohol matrix material in the step (1) can be replaced by one or more of polyethylene glycol, polyvinylpyrrolidone, polystyrene sulfonic acid, polyallylamine, polyvinyl amine, polyquaternium, carboxymethyl starch, starch acetate, sodium polyacrylate, guar gum and polyaspartic acid.
The reaction temperature in the step (2) is 60 ℃, and the concentration of the excessive N, N-carbonyl diimidazole is 0.5-5wt% of the polyvinyl alcohol.
The cellulose nanocrystalline in the step (2) can be one or more of carboxymethyl cellulose nanocrystalline, methyl cellulose nanocrystalline, ethyl cellulose nanocrystalline and hydroxyethyl cellulose nanocrystalline; the length of the cellulose nanocrystalline is 100-1000 nanometers, and the diameter is 5-30 nanometers.
The reaction temperature in the step (3) is 60-80 ℃, and the concentration of the excessive N, N-carbonyl diimidazole is 0.5-5wt% of the polyvinyl alcohol.
The polyrotaxane in the step (3) is one or more of polyisoprene/alpha-cyclodextrin, poly (ethylene glycol)/alpha-cyclodextrin, N- [ tri (hydroxymethyl) methyl ] acrylamide/alpha-cyclodextrin, methyl propylene-2-hydroxyethyl/alpha-cyclodextrin, poly (ethylene oxide)/alpha-cyclodextrin and poly (propylene oxide)/alpha-cyclodextrin.
The reaction temperature in the step (4) is 60-80 ℃.
The coagulating bath adopted in the step (5) is one or more of ethanol/methanol/acetic acid/ethyl acetate/water.
And (5) adopting a thermal traction mode of fixed-length thermal stretching.
The slipping mechanical interlocking network taking polyrotaxane as a crosslinking point means that alpha-cyclodextrin with hydroxyl on a polyrotaxane ring and hydroxyl on a polyvinyl alcohol molecular chain undergo chemical crosslinking reaction through N, N-carbonyl diimidazole to form a chemical covalent bond. When the artificial spider silk is subjected to tensile deformation under stress, the crosslinking point formed between the main chain of the matrix and the polywheel ring is cooperated with the stretching action of the polywheel ring molecular chain, so that the alpha-cyclodextrin slides along the main chain of the polyethylene oxide molecule to generate a roller-skating effect, dissipate the stress and improve the tensile strain and toughness of the fiber.
The rigid network taking the cellulose nanocrystal as a crosslinking point means that hydroxyl carboxyl on the cellulose nanocrystal and hydroxyl on a polyvinyl alcohol molecular chain undergo a chemical crosslinking reaction through N, N-carbonyl diimidazole to form a chemical covalent bond. When the artificial spider silk is subjected to stress and tensile deformation, a strong cross-linking point is formed between the main chain of the matrix and the cellulose nanocrystalline, so that the movement of a molecular chain is prevented, a large amount of stress is absorbed, and the strength and the rigidity of the fiber are improved.
The diameter of the artificial spider silk fiber is 1-10 micrometers, the elongation at break is more than 60 percent, the breaking strength is more than 1GPa, and the toughness is more than 400MJ/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The fiber has a rapid shape memory function.
The artificial spider silk fiber can be applied to the fields of impact resistance, safety protection, flexible electronics, high-performance composite materials and the like.
The invention has the advantages and beneficial effects that:
1. the raw materials of polyvinyl alcohol, polyrotaxane and cellulose nanocrystalline used in the invention have low cost, are degradable and are environment-friendly.
2. The artificial spider silk prepared by the invention is prepared by a wet spinning process and a heat treatment process, and the preparation method is simple and can be used for mass production.
3. The high-strength high-toughness artificial spider silk with double cross-linked networks prepared by the invention has a rigid network with cellulose nanocrystals as cross-linked points and a slidable mechanical interlocking network fiber with polyrotaxane as the cross-linked points. Wherein the rigid network increases the strength of the fiber and the slidable mechanical interlocking network increases the toughness of the fiber. The synergistic effect of the double networks gives good mechanical properties to the artificial spider silk.
4. The elongation at break of the artificial spider silk obtained by the invention is more than 60 percent, the breaking strength is more than 1GPa, and the toughness is more than 400MJ/m 3 The method comprises the steps of carrying out a first treatment on the surface of the And has a rapid shape memory function.
5. The artificial spider silk obtained by the invention has similar structure with natural spider silk, and opens up a new way for the high polymer material in the bionic field.
Drawings
Fig. 1 is a macroscopic view of an artificial spider silk fiber of the present invention.
Fig. 2 is a scanning electron microscope image of an artificial spider silk fiber of the present invention.
Fig. 3 is a graph of the mechanical properties of an artificial spider silk fiber of the present invention.
Fig. 4 is a graph showing the mechanical properties of the artificial spider silk fiber of the present invention.
Fig. 5 is a diagram showing the shape memory characteristics of the artificial spider silk fiber of the present invention.
Detailed Description
The invention is further described below in conjunction with the detailed description. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1:
(1) 224mg of polyvinyl alcohol (mw=20,000) was weighed out and dissolved in 1ml of anhydrous dimethyl sulfoxide, and heated and stirred at 80 ℃ for 2 hours. Forming a uniform dispersion with a concentration of 20wt%;
(2) 2.24mg of cellulose nanocrystals are weighed and dispersed in 0.5ml of anhydrous dimethyl sulfoxide to form uniform dispersion liquid, the concentration is 1wt% of polyvinyl alcohol, 2.24mg of N, N-carbonyl diimidazole is added, the mixture is uniformly mixed and then is placed in an environment of 60 ℃ for heat preservation for 5 hours, and N, N-carbonyl diimidazole reacts with hydrophilic functional groups on the surface of the cellulose nanocrystals to form an intermediate;
(3) 2.24mg of polyrotaxane is weighed and dispersed in 0.5ml of anhydrous dimethyl sulfoxide to form uniform dispersion liquid, the concentration is 1wt% of polyvinyl alcohol, 2.24mg of N, N-carbonyl diimidazole is added, the mixture is uniformly mixed, and then the mixture is placed in an environment of 60 ℃ for heat preservation for 5 hours, and N, N-carbonyl diimidazole reacts with hydrophilic functional groups on the surface of polyrotaxane to form an intermediate;
(4) And mixing the dispersibility, and stirring for 2 hours at 60 ℃ to obtain the composite spinning solution. Forming a rigid network taking cellulose nanocrystals as crosslinking points and a slidable mechanical interlocking network taking polyrotaxane as the crosslinking points;
(5) Extruding the composite spinning solution through a spinning die head, solidifying through a methanol coagulating bath, and collecting through a roll shaft to form self-supporting nascent fibers; and (3) placing the primary composite fiber in a 210 ℃ oven for continuous thermal traction, wherein the stretching multiplying power is 4 times, and the heating time is 2 minutes, so that the final artificial spider silk fiber is obtained. Fig. 1 is a photograph of the obtained artificial spider silk fiber, and fig. 2 shows a scanning electron microscope image of the obtained artificial spider silk fiber.
The artificial spider silk fibers finally obtained in this example were subjected to the following tests:
mechanical property test, the artificial spider silk fiber with the diameter of 5 micrometers is subjected to a tensile test (the tensile rate is 10 mm/min) under the condition of 40% of air humidity, as shown in figure 3, the artificial spider silk obtained by the example has the elongation at break of more than 60%, the breaking strength of more than 1GPa and the toughness of more than 400MJ/m3;
example 2:
(1) 112mg of polyvinyl alcohol (mw=20,000) was weighed out and dissolved in 1ml of anhydrous dimethyl sulfoxide, and heated and stirred at 80 ℃ for 2 hours. Forming a uniform dispersion with a concentration of 10wt%;
(2) 2.24mg of cellulose nanocrystals are weighed and dispersed in 0.5ml of anhydrous dimethyl sulfoxide to form uniform dispersion liquid, the concentration is 2wt% of polyvinyl alcohol, 2.24mg of N, N-carbonyl diimidazole is added, the mixture is uniformly mixed and then is placed in an environment of 60 ℃ for heat preservation for 5 hours, and N, N-carbonyl diimidazole reacts with hydrophilic functional groups on the surface of the cellulose nanocrystals to form an intermediate;
(3) 2.24mg of polyrotaxane is weighed and dispersed in 0.5ml of anhydrous dimethyl sulfoxide to form uniform dispersion liquid, the concentration is 2wt% of polyvinyl alcohol, 2.24mg of N, N-carbonyl diimidazole is added, the mixture is uniformly mixed, and then the mixture is placed in an environment of 60 ℃ for heat preservation for 5 hours, and N, N-carbonyl diimidazole reacts with hydrophilic functional groups on the surface of polyrotaxane to form an intermediate;
(4) And mixing the dispersibility, and stirring for 2 hours at 60 ℃ to obtain the composite spinning solution. Forming a rigid network taking cellulose nanocrystals as crosslinking points and a slidable mechanical interlocking network taking polyrotaxane as the crosslinking points;
(5) Extruding the composite spinning solution through a spinning die head, solidifying the composite spinning solution through an ethanol coagulating bath, and collecting the composite spinning solution through a roll shaft to form self-supporting nascent fibers; and (3) placing the primary composite fiber in a 210 ℃ oven for continuous thermal traction, wherein the stretching multiplying power is 2 times, and the heating time is 4 minutes, so as to obtain the final artificial spider silk fiber.
The artificial spider silk obtained in this example was subjected to the following tests:
mechanical display As shown in FIG. 4, a 5cm artificial spider silk was taken and allowed to withstand a 5g weight rotating at 160rpm under conditions of 40% air humidity.
Example 3:
(1) 224mg of polyvinyl alcohol (mw=20,000) was weighed out and dissolved in 1ml of anhydrous dimethyl sulfoxide, and heated and stirred at 80 ℃ for 2 hours. Forming a uniform dispersion with a concentration of 20wt%;
(2) Weighing 4.48mg of cellulose nanocrystals, dispersing in 0.5ml of anhydrous dimethyl sulfoxide to form a uniform dispersion, adding 2.24mg of N, N-carbonyl diimidazole, uniformly mixing, and then placing the mixture in a 60 ℃ environment for heat preservation for 5 hours to enable the N, N-carbonyl diimidazole to react with hydrophilic functional groups on the surface of the cellulose nanocrystals to form an intermediate;
(3) 4.48mg of polyrotaxane is weighed and dispersed in 0.5ml of anhydrous dimethyl sulfoxide to form uniform dispersion liquid, the concentration is 2wt% of polyvinyl alcohol, 2.24mg of N, N-carbonyl diimidazole is added, the mixture is uniformly mixed, and then the mixture is placed in an environment of 60 ℃ for heat preservation for 5 hours, and N, N-carbonyl diimidazole reacts with hydrophilic functional groups on the surface of polyrotaxane to form an intermediate;
(4) And mixing the dispersibility, and stirring for 2 hours at 60 ℃ to obtain the composite spinning solution. Forming a rigid network taking cellulose nanocrystals as crosslinking points and a slidable mechanical interlocking network taking polyrotaxane as the crosslinking points;
(5) Extruding the composite spinning solution through a spinning die head, solidifying the composite spinning solution through an ethanol coagulating bath, and collecting the composite spinning solution through a roll shaft to form self-supporting nascent fibers; and (3) placing the nascent composite fiber in a 190 ℃ oven for continuous thermal traction, wherein the stretching multiplying power is 6 times, and the heating time is 4 minutes, so as to obtain the final artificial spider silk fiber.
The artificial spider silk obtained in this example was subjected to the following tests:
the shape memory characteristics are shown in figure 5. The artificial spider silk is woven into a spider web, and one 50g egg is freely dropped at a height of 25cm, and the spider web can withstand the impact of the egg and quickly recover after removing the egg.
Claims (9)
1. A method for preparing artificial spider silk based on double cross-linked network, which is characterized in that: respectively taking cellulose nanocrystals and polyrotaxane as cross-linking agents, and forming a rigid network taking the cellulose nanocrystals as cross-linking points and a chemical cross-linking double-network structure of a slidable mechanical interlocking network taking the polyrotaxane as the cross-linking points in a fiber matrix;
the rigid network taking the cellulose nanocrystals as the crosslinking points means that hydroxyl carboxyl groups on the cellulose nanocrystals and hydroxyl groups on a polyvinyl alcohol molecular chain undergo chemical crosslinking reaction through N, N-carbonyl diimidazole to form chemical covalent bonds, and when the artificial spider silk is subjected to stress and tensile deformation, strong crosslinking points are formed between a matrix main chain and the cellulose nanocrystals, so that the movement of the molecular chain is prevented, a large amount of stress is absorbed, and the strength and rigidity of the fiber are improved;
the slipping mechanical interlocking network taking polyrotaxane as a crosslinking point means that alpha-cyclodextrin with hydroxyl on a polyrotaxane and hydroxyl on a polyvinyl alcohol molecular chain undergo chemical crosslinking reaction through N, N-carbonyl diimidazole to form a chemical covalent bond, when the artificial spider silk is subjected to stress and tensile deformation, the crosslinking point formed between a matrix main chain and the polyrotaxane is cooperated with the stretching action of the polyrotaxane molecular chain, so that the alpha-cyclodextrin slips along the polyethylene oxide molecular main chain to generate a roller sliding effect, dissipate stress and improve the tensile strain and toughness of fibers;
the preparation method comprises the following preparation steps:
(1) Dissolving a polyvinyl alcohol matrix raw material into anhydrous dimethyl sulfoxide to form a uniform dispersion liquid, wherein the concentration is 5-20wt%;
(2) Dispersing cellulose nanocrystals in anhydrous dimethyl sulfoxide to form a uniform dispersion liquid, wherein the concentration is 0.1-3wt% of polyvinyl alcohol, and adding excessive N, N-carbonyl diimidazole to react with hydrophilic functional groups on the surface of the cellulose nanocrystals to form an intermediate;
(3) Dispersing polyrotaxane in anhydrous dimethyl sulfoxide to form uniform dispersion with the concentration of 0.1-10wt% of polyvinyl alcohol, and adding excessive N, N-carbonyl diimidazole to react with hydrophilic functional groups on the surface of cellulose nanocrystals to form an intermediate;
(4) Mixing the dispersibility, and further performing a crosslinking reaction to form a rigid network taking cellulose nanocrystals as crosslinking points and a slidable mechanical interlocking network taking polyrotaxane as the crosslinking points, thereby obtaining a composite spinning solution;
(5) Extruding the composite spinning solution through a spinning die head, solidifying through a poor solvent coagulating bath, and collecting by a roll shaft to form self-supporting nascent fibers; and (3) placing the nascent composite fiber in a baking oven at 180-220 ℃ for continuous thermal traction, wherein the stretching multiplying power is 2-12 times, and the heating time is 2-10 minutes, so as to obtain the final artificial spider silk fiber.
2. A method of preparing artificial spider silk based on double cross-linked networks according to claim 1, characterized in that: the polyrotaxane is one or more of polyisoprene/alpha-cyclodextrin, poly (ethylene glycol)/alpha-cyclodextrin, N- [ tri (hydroxymethyl) methyl ] acrylamide/alpha-cyclodextrin, methacrylic acid-2-hydroxyethyl/alpha-cyclodextrin, poly (ethylene oxide)/alpha-cyclodextrin and poly (propylene oxide)/alpha-cyclodextrin.
3. A method of preparing artificial spider silk based on double cross-linked networks according to claim 1, characterized in that: the cellulose nanocrystalline is one or more of carboxymethyl cellulose nanocrystalline, methyl cellulose nanocrystalline, ethyl cellulose nanocrystalline and hydroxyethyl cellulose nanocrystalline; the length of the cellulose nanocrystalline is 100-1000 nanometers, and the diameter is 5-30 nanometers.
4. A method of preparing artificial spider silk based on double cross-linked networks according to claim 1, characterized in that: the molecular weight of the polyvinyl alcohol matrix used is 50,000-500,000.
5. A method of preparing artificial spider silk based on double cross-linked networks according to claim 1, characterized in that: the polyvinyl alcohol matrix material is replaced by one or more of polyethylene glycol, polyvinylpyrrolidone, polystyrene sulfonic acid, polyallylamine, polyvinyl amine, polyquaternary ammonium salt, carboxymethyl starch, acetic acid starch, sodium polyacrylate, guar gum and polyaspartic acid.
6. A method of preparing artificial spider silk based on double cross-linked networks according to claim 1, characterized in that: the reaction temperature in the step (3) is 60-80 ℃, and the concentration of the excessive N, N-carbonyl diimidazole is 0.5-5wt% of the polyvinyl alcohol;
the reaction temperature in the step (4) is 60-80 ℃;
the coagulating bath adopted in the step (5) is one or more of ethanol/methanol/acetic acid/ethyl acetate/water, and the adopted thermal traction mode is fixed-length thermal stretching.
7. An artificial spider silk fiber, characterized in that: prepared by the process of any one of claims 1-6.
8. The artificial spider silk fiber according to claim 7, wherein: the diameter of the fiber is 1-10 micrometers, the elongation at break is more than 50%, the breaking strength is more than 1GPa, and the toughness is more than 350MJ/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The fiber has a rapid shape memory function.
9. Use of the artificial spider silk fiber according to claim 7 or 8 for the preparation of impact resistant, safety protective, flexible electronic, high performance composite materials.
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