CN113638078B - Polyelectrolyte complex hydrogel fiber and preparation method thereof - Google Patents
Polyelectrolyte complex hydrogel fiber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyelectrolyte complex hydrogel fiber and a preparation method thereof, the method comprises the steps of firstly taking a solution X as a spinning solution to carry out wet spinning, after being compounded by a coagulating bath, completely immersing the fiber into a solution containing polyvalent metal ions C for treatment, and finally carrying out water absorption treatment to obtain the fiber; when the solution X is a solution in which the polycationic electrolyte a is a solute, the solute of the solution Y as a coagulation bath is a polyanionic electrolyte B; when the solution X is a solution with polyanionic electrolyte B as a solute, the solute of the solution Y as a coagulation bath is polycationic electrolyte A; the prepared fiber has a skin-core structure, electrostatic force is formed between the skin layer and the core layer, and carboxylate radicals in the polyanionic electrolyte B and polyvalent metal ions C form a coordination crosslinking structure; hydrogel fibers were completely immersed in deionized water and tested after 2 days of immersion: the elongation at break is 80-160%, the monofilament strength is 10-45 MPa, the initial modulus is 12-180 MPa, and a weight 2-1 ten thousand times of the self weight can be pulled.
Description
Technical Field
The invention belongs to the technical field of hydrogel fibers, relates to a polyelectrolyte complex hydrogel fiber and a preparation method thereof, and particularly relates to a polyelectrolyte complex hydrogel fiber applicable to artificial tendon tissue and a preparation method thereof.
Background
Hydrogels are a class of materials with good biocompatibility and softness, have a three-dimensional network structure with extremely high hydrophilic capacity, can swell rapidly in water and can hold a large volume of water in this swollen state without dissolving. The material has high water content, good biocompatibility and easy modification, and can realize reversible expansion and contraction under the stimulation of some factors (such as pH and temperature). Hydrogels are commonly used as adsorbents, drug carriers, and the like, and have important applications in the fields of drug therapy, biological detection, and the like. However, the mechanical properties and anti-swelling ability of conventional hydrogels are generally poor, resulting in limited practical applications thereof.
In recent years, the construction of hydrogels with a double network structure and hydrogels with interpenetrating network structures have become a focus of research. A strong network structure and a weak network structure are constructed in a hydrogel network system, the strong network plays a role in maintaining the integrity of the network structure, and the weak network plays a role in dissipating energy, so that the mechanical property of the hydrogel can be improved. Or constructing a hybrid hydrogel with nanoparticles can also improve the toughness and strength of the hydrogel. The loaded nano composite gel has the characteristics of both nano materials and gel, and the synergistic enhancement of the components can be realized after the nano composite gel is compounded. However, the above methods generally use organic solvents or have complicated chemical synthesis steps, which destroy the chemical properties of the original hydrogel, and the nanoclusters are easily agglomerated during the gelation process, thereby greatly affecting the use of the hydrogel. How to construct hydrogel with excellent mechanical properties by a green and simple method becomes a hot point for research and development of extensive researchers.
Polyelectrolyte complexes have different characteristics from those of common polymer materials, and are often used for the preparation of hydrogels due to their biocompatibility. The surface of which is charged, making polyelectrolyte complexes often very sensitive to conditions of temperature, pH, humidity, etc. This property often results in poor mechanical properties of the polyelectrolyte complex when used as a hydrogel.
Therefore, the research on the polyelectrolyte composite hydrogel fiber with simple preparation method and good mechanical property and the preparation method thereof have very important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a polyelectrolyte complex hydrogel fiber and a preparation method thereof. By utilizing a method combining interface compounding and wet spinning, a polycation electrolyte solution is extruded into a polyanion electrolyte solution as a spinning solution, or the polyanion electrolyte solution is extruded into the polycation electrolyte solution as the spinning solution, and at the moment, the interface of the polyanion electrolyte solution and the polycation electrolyte solution which are in mutual contact is compounded due to electrostatic interaction, so as to assist the fiber to be formed, and the polyelectrolyte composite fiber with a skin-core structure is obtained; and then the polyelectrolyte composite fiber is further subjected to coordination crosslinking, so that the polyelectrolyte composite hydrogel fiber with an electrostatic force crosslinking network and a coordination crosslinking network can be obtained, and the polyelectrolyte composite hydrogel fiber has excellent performance.
In order to achieve the purpose, the invention adopts the following scheme:
a polyelectrolyte complex hydrogel fiber comprises a polyelectrolyte complex fiber and polyvalent metal ions C in the polyelectrolyte complex fiber;
the polyelectrolyte composite fiber has a skin-core structure, and electrostatic force is formed between the skin layer and the core layer; when the skin layer is the polycation electrolyte A, the core layer is the polyanion electrolyte B; when the core layer is the polycation electrolyte A, the skin layer is the polyanion electrolyte B;
the carboxylate in the polyanionic electrolyte B in the polyelectrolyte composite fiber and the polyvalent metal ion C form a coordination crosslinking structure (if no coordination interaction is introduced, although the polyelectrolyte composite fiber can still be used as a hydrogel fiber, the polyelectrolyte composite fiber has extremely poor mechanical properties and is not suitable for subsequent applications, such as being not used for imitating artificial tendon tissue and the like).
As a preferable technical scheme:
the mass ratio of the polyelectrolyte forming the skin layer to the polyelectrolyte forming the core layer of the polyelectrolyte composite hydrogel fiber is 1-2; the mass ratio of the polyanionic electrolyte B to the multivalent metal ions C is 8-12.
In the polyelectrolyte composite hydrogel fiber, the polycation electrolyte A is more than one of chitosan, polyallylamine and polydiallyldimethylammonium chloride, and the multi-component compounding process is complex and the performance is not greatly improved, so that a single polymer is preferably used; the polyanion electrolyte B is more than one of sodium alginate, N-dicarboxymethyl polyallylamine, N-dicarboxymethyl branched polyethyleneimine and N, N-dicarboxymethyl-based polyethyleneimine, and the multi-component compounding process is complex and the performance is not greatly improved, so that a single polymer is preferably used.
The polyelectrolyte complex hydrogel fiber has the advantages that the polyvalent metal ion C is Ca 2+ 、Fe 3+ 、Cu 2+ 、Zn 2+ 、Ce 3+ 、Eu 3+ Or Tb 3+ When the polyvalent metal ion added is Ca 2+ 、Fe 3+ 、Cu 2+ Or Zn 2+ When the metal ions are used, a small amount of the metal ions are harmless to human bodies and can be widely applied; when the added polyvalent metal ion is Ce 3+ 、Eu 3+ Or Tb 3+ Such metals can then be used to prepare fluorescent hydrogel fibers; although coordination crosslinking can be formed by adding a plurality of polyvalent metal ions, the polyvalent metal ions with weak coordination ability hardly participate in coordination due to the competitive relationship among the metal ions, and even if added, beneficial contribution in performance cannot be generated.
The polyelectrolyte complex hydrogel fiber has the monofilament diameter of 50-75 microns, the elongation at break of 10-160%, the monofilament strength of 10-230 MPa and the initial modulus of 12-4000 MPa; the mechanical properties of the hydrogel fibers can be greatly changed due to different water contents of the hydrogel fibers, and the properties listed here are the range of the mechanical properties of the hydrogel fibers after water is fully absorbed from low water content;
completely soaking the polyelectrolyte complex hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days to obtain: the elongation at break is 80-160%, the monofilament strength is 10-45 MPa, the initial modulus is 12-180 MPa, and a heavy object with the weight of 2-1 ten thousand times of the self weight can be pulled. The elongation at break, the monofilament strength and the initial modulus are obtained by testing with a monofilament strength tensile tester, and the test standard is shown in DOI:10.1021/acsapm.0c00056.
The invention also provides a method for preparing the polyelectrolyte composite hydrogel fiber, which comprises the steps of firstly carrying out wet spinning by using the polyelectrolyte solution X as a spinning solution, and compounding by using a coagulating bath to obtain the polyelectrolyte composite fiber (the method is similar to the wet spinning, the coagulating bath is a polyelectrolyte solution with opposite charges, and the method can form the composite while compounding, and cannot be processed into the fiber if the coagulating bath is not adopted); completely soaking the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment, and finally placing the fiber under a certain humidity or soaking the fiber in water for water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber;
when the polyelectrolyte solution X is a solution with polycation electrolyte A as a solute, the solute of the polyelectrolyte solution Y as a coagulation bath is polyanion electrolyte B;
when the polyelectrolyte solution X is a solution having a polyanionic electrolyte B as a solute, the solute of the polyelectrolyte solution Y as a coagulation bath is a polycationic electrolyte a.
The spinning solution is subjected to centrifugal deaeration before spinning.
The polycation electrolyte A and the polyanion electrolyte B can form a polyelectrolyte complex due to electrostatic interaction; a large number of carboxylate groups exist in the polyanion electrolyte B, and the polyanion electrolyte B can form a polyelectrolyte compound with the polycation electrolyte A due to electrostatic interaction and can also form coordination crosslinking with the metal ions C.
The water absorption treatment means: placing the fiber in a constant temperature and humidity box under different humidity, wherein the water content can reach 0-15%; the fiber is put in water for different time, and the water content can reach between 15 and 88 percent. At the same time, the excess inorganic salts and the like on the surface can also be removed.
As a preferred technical scheme:
in the method, the mass fractions of the polyelectrolytes in the polyelectrolyte solution X and the polyelectrolyte in the polyelectrolyte solution Y are both 0.5 to 1.5wt.%; the polyelectrolyte solution X and the polyelectrolyte solution Y are prepared by dissolving polyelectrolyte in water with certain pH value, and the polyelectrolyte is in a complete dissolved state, wherein acid for adjusting the pH value is hydrochloric acid and/or acetic acid, and alkali is sodium hydroxide; when the concentration of the spinning solution (polyelectrolyte solution X) is too high, the viscosity is too high, the spinning solution is not suitable for extrusion, the concentration is too low, and the fluid is unstable during extrusion; when the concentration of the coagulation bath (polyelectrolyte solution Y) is too high, the spinning solution can not stably flow in the coagulation bath, the concentration is too low, and the compounding process is slow;
the concentration of the solution containing the metal ion C is 1-2 mg/mL, and the excessive surface adsorption of the excessive metal ion is caused when the concentration of the solution containing the metal ion C is too high, and the efficiency of coordination and recombination is influenced when the concentration is too low.
According to the method, the residence time of the extruded spinning solution in the coagulating bath is 15 min-24 h; the time is too low, the fiber compounding process is incomplete, and the fiber performance is poor; the time reaches 24h, the compounding process is basically completed, and more benefits cannot be generated after the time is prolonged. The technological parameters of wet spinning are as follows: the extrusion speed is 0.8mL/min, the spinneret orifice type is 20mm long, the outer diameter is 0.31mm, and the inner diameter is 0.13mm.
In the method, the polyelectrolyte composite fiber is completely immersed in the solution containing the polyvalent metal ions C for less than or equal to 24 hours. At this time, the polyvalent metal ion C in the solution containing the polyvalent metal ion C diffuses into the fiber, and the fibers with different coordination amounts can be obtained at different impregnation times due to the strong coordination interaction between the carboxylic acid and the metal in the polyelectrolyte composite fiber.
In the method, the polyelectrolyte composite fiber is washed with water for 10-30 s and then completely immersed in the solution containing the polyvalent metal ions C, and the purpose of the water washing is to remove the excessive acid, alkali and polyelectrolyte on the surface.
The principle of the invention is as follows:
the concentrations of the polycationic electrolyte a (hereinafter, abbreviated as a) and the polyanionic electrolyte B (hereinafter, abbreviated as B) of the present invention are 0.5 to 1.5wt.%, and a and B can form a polyelectrolyte complex in an aqueous solution by electrostatic interaction. In the method for preparing polyelectrolyte composite fibers researched in the prior art, an interface drafting method is adopted, two liquid drops A and B are contacted with each other to form a composite layer on a contact interface, and then the composite layer is drafted manually. The invention combines interface recombination and wet spinning, as shown in figure 1, firstly, the solution A is extruded into the solution B through a spinneret orifice, and when the solution A and the solution B just contact, a layer of compound protective film is formed on the surface of the fluid A due to the electrostatic interaction of the solution A and the solution B, thereby protecting the stability of the fluid A. Along with the prolonging of the compounding time in the solution B, more solution B diffuses inwards to be compounded with the solution A, the conformational entropy is reduced, more water molecules are extruded out of the system, and finally the polyelectrolyte composite fiber with the core layer of A and the skin layer of B is formed. Similarly, if the solution B is extruded into the solution a as a spinning solution, the polyelectrolyte composite fiber with the core layer B and the skin layer a is finally formed, and electrostatic force is formed between the skin layer and the core layer (as shown in fig. 2). And then immersing the polyelectrolyte composite fiber into a solution of the polyvalent metal ion C, wherein 2 oxygens in the carboxylate radicals are resonant and can be used as coordination atoms, so that the polyvalent metal ion C and the carboxylate radicals in the polyvalent metal ion B form coordination bonds (as shown in FIG. 3), and the bond energy of the coordination bonds is between covalent bonds and ionic bonds, so that a strong cross-linked network structure can be formed.
Water molecules entering the polyelectrolyte complex can be used as a plasticizer to change the mechanical properties of the polyelectrolyte complex. When a small amount of water molecules enter the polyelectrolyte complex, the molecular chain movement space is increased due to the lubricating effect, the whole chain moves more freely, and the macro expression of the material is that the material becomes softer. When more water molecules enter the polyelectrolyte compound, the water molecules and some polar groups in the polymer generate stronger hydrogen bond action, ion pairs (polycation and polyanion ion pairs) generated by compounding are damaged, and the material macroscopically shows that the material is further swelled and even decomposed for a long time. After the coordination bonds are introduced, the polyvalent metal ions and the carboxylate radicals in the polyanion generate strong crosslinking, and the bonding strength of the coordination bonds is between that of the ionic bonds and the covalent bonds, so that the coordination network can be used as a strong network to maintain the integrity of the material. Therefore, the finally prepared hydrogel fiber can have good mechanical strength in a water environment.
Advantageous effects
(1) The preparation method of the polyelectrolyte complex hydrogel fiber constructs the hydrogel fiber with excellent mechanical property in a green and simple way, the mechanical property can be comparable to muscle fiber in muscle tissue, the monofilament strength of the hydrogel fiber can be adjusted between 10-230 MPa, the corresponding elongation can be adjusted between 10-160%, the initial modulus is 12-180 MPa in water environment for a long time, 2 thousand-1 ten thousand times of weight can be pulled, and each property is in accordance with the use of artificial tendon tissue (the mechanical strength of the muscle fiber in human tendon tissue is 0.35MPa at most, the elongation is 20%, the modulus is 10-60 MPa), and the preparation method is expected to be applied in the field of artificial tendon;
(2) The preparation method of the polyelectrolyte complex hydrogel fiber can effectively control the mechanical property of the hydrogel fiber, and can obtain hydrogel fibers with different coordination crosslinking ratios by changing the time for soaking the polyvalent metal ion solution;
(3) The polyelectrolyte complex hydrogel fiber prepared by the method disclosed by the invention is excellent in mechanical property, can still have good mechanical strength in a water environment, and has a wide application prospect.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic representation of the electrostatic forces of the skin and core layers in the coagulation bath of the present invention;
FIG. 3 is a schematic diagram showing a coordination structure in coordination crosslinking in the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example A1
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving chitosan in an acetic acid solution, adjusting the pH value of the solution to 3.5, and then performing centrifugal deaeration to obtain a polyelectrolyte solution X with the mass fraction of 1.5wt.% of polyelectrolyte;
polyelectrolyte solution Y: dissolving sodium alginate in deionized water, and centrifuging and defoaming to obtain a polyelectrolyte solution Y with the mass fraction of 1.5wt.% of polyelectrolyte;
solution containing metal ion C: adding CaCl 2 Dissolving in deionized water to obtain a solution containing metal ions C with the concentration of 1 mg/mL;
(2) Carrying out wet spinning by taking a polyelectrolyte solution X as a spinning solution, compounding for 24 hours by taking a polyelectrolyte solution Y as a coagulating bath, and then washing for 20 seconds to obtain a polyelectrolyte composite fiber with a skin-core structure; electrostatic force is formed between the skin layer and the core layer, the core layer is made of chitosan, and the skin layer is made of sodium alginate; the mass ratio of the sodium alginate forming the skin layer to the chitosan forming the core layer is 1;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 1 hour, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 70% and still maintaining the skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, carboxylate radicals in sodium alginate and polyvalent metal ions C form a coordination crosslinking structure, and the sodium alginate and the polyvalent metal ions C (Ca) 2+ ) The mass ratio of (2).
The properties of the polyelectrolyte complex hydrogel fiber were tested as follows: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 160%, the monofilament strength is 10MPa, the initial modulus is 15MPa, and a weight which is 2 thousand times of the self weight can be pulled.
Comparative example 1
A method for preparing a polyelectrolyte complex hydrogel fiber, which comprises the same steps as those of example A1, except that the polyelectrolyte complex fiber prepared in step (2) was directly tested without performing step (3), and the results were as follows:
the structure of the polyelectrolyte complex fiber was the same as in example A1, but the polyelectrolyte complex hydrogel fiber had the following properties: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 200%, the monofilament strength is 0.1MPa, the initial modulus is 0.05MPa, and a weight 10 times of the self weight can be pulled.
Example A2
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving polyallylamine in deionized water, adjusting the pH value to 3.5, and performing centrifugal defoaming to obtain a polyelectrolyte solution X with the mass fraction of 0.8wt.% of polyelectrolyte;
polyelectrolyte solution Y: dissolving N, N-dicarboxymethylpolyallylamine in deionized water, adjusting the pH value to 3.5, and centrifuging and defoaming to obtain a polyelectrolyte solution Y with the mass fraction of 1wt.% of polyelectrolyte;
solution containing metal ion C: feCl is added 3 Dissolving in deionized water to obtain a solution containing metal ion C with the concentration of 1.5 mg/mL;
(2) Carrying out wet spinning by taking polyelectrolyte solution X as spinning solution, compounding for 18 hours by taking polyelectrolyte solution Y as coagulating bath, and then washing for 15 seconds to obtain the polyelectrolyte composite fiber with a skin-core structure; electrostatic force is formed between the skin layer and the core layer, the core layer is polyallylamine, and the skin layer is N, N-dicarboxymethylpolyallylamine; the mass ratio of the skin layer to the core layer is 1;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 2 hours, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 65% and still maintaining the skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, carboxylate radicals in N, N-dicarboxymethylpolyallylamine and polyvalent metal ions C form a coordination crosslinking structure, and the N, N-dicarboxymethylpolyallylamine and the polyvalent metal ions C (Fe) 3+ ) The mass ratio of (2).
The properties of the polyelectrolyte complex hydrogel fiber were tested as follows: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 150%, the monofilament strength is 20MPa, the initial modulus is 30MPa, and a weight 4 thousand times of the self weight can be lifted.
Example A3
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving poly (diallyldimethylammonium chloride) in deionized water, adjusting the pH value to 3, and performing centrifugal defoaming to obtain a polyelectrolyte solution X with the mass fraction of 1.2wt.% of polyelectrolyte;
polyelectrolyte solution Y: dissolving N, N-dicarboxymethyl branched polyethyleneimine in deionized water, adjusting the pH value to 3, and performing centrifugal deaeration to obtain a polyelectrolyte solution Y with the mass fraction of 1.5wt.% of polyelectrolyte;
solution containing metal ion C: mixing EuCl 3 Dissolving in deionized water to obtain a solution containing metal ions C with the concentration of 1 mg/mL;
(2) Carrying out wet spinning by taking polyelectrolyte solution X as spinning solution, compounding for 12 hours by taking polyelectrolyte solution Y as coagulating bath, and then washing for 25 seconds to obtain the polyelectrolyte composite fiber with a skin-core structure; electrostatic force is formed between the skin layer and the core layer, the core layer is poly diallyl dimethyl ammonium chloride, and the skin layer is N, N-dicarboxymethyl branched polyethyleneimine; the mass ratio of the skin layer to the core layer is 2;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 5 hours, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 75% and still maintaining the skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, carboxylate radicals in the N, N-dicarboxymethyl branched polyethyleneimine and polyvalent metal ions C form a coordination crosslinking structure, and the N, N-dicarboxymethyl branched polyethyleneimine and the polyvalent metal ions C (Eu) 3+ ) The mass ratio of (1).
The performance of the polyelectrolyte complex hydrogel fiber is tested as follows: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 140%, the monofilament strength is 15MPa, the initial modulus is 25MPa, and a weight 3 thousand times of the self weight can be pulled.
Example A4
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving a mixture of chitosan and polyallylamine in a mass ratio of 1;
polyelectrolyte solution Y: dissolving N, N-dicarboxyl baseline polyethyleneimine in deionized water, adjusting the pH value to 3, and performing centrifugal deaeration to obtain a polyelectrolyte solution Y with the mass fraction of 1wt.% of polyelectrolyte;
solution containing metal ion C: adding CuCl 2 Dissolving in deionized water to obtain a solution containing metal ions C with the concentration of 1.2 mg/mL;
(2) Carrying out wet spinning by taking polyelectrolyte solution X as spinning solution, compounding for 24 hours by taking polyelectrolyte solution Y as coagulating bath, and then washing for 30 seconds to obtain the polyelectrolyte composite fiber with a skin-core structure; electrostatic force is formed between the skin layer and the core layer, the core layer is a mixture of chitosan and polyallylamine with the mass ratio of 1; the mass ratio of the skin layer to the core layer is 2;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 6 hours, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 75% and still maintaining a skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, carboxylate radicals in N, N-dicarboxyl-based polyethyleneimine and polyvalent metal ions C form a coordination crosslinking structure, and the N, N-dicarboxyl-based polyethyleneimine and the polyvalent metal ions C (Cu) 2+ ) The mass ratio of (1).
The performance of the polyelectrolyte complex hydrogel fiber is tested as follows: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 160%, the monofilament strength is 10MPa, the initial modulus is 12MPa, and a weight 2 thousand times of the self weight can be pulled.
Example A5
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving chitosan in an acetic acid solution, adjusting the pH value of the solution to 3.5, and performing centrifugal defoaming to obtain a polyelectrolyte solution X with the mass fraction of 1.5wt.% of polyelectrolyte;
polyelectrolyte solution Y: dissolving a mixture of sodium alginate and N, N-dicarboxymethylpolyallylamine in a mass ratio of 1:1 in deionized water, adjusting the pH value to 3, and performing centrifugal deaeration to obtain a polyelectrolyte solution Y with the mass fraction of polyelectrolyte of 1.5wt.%;
solution containing metal ion C: reacting ZnCl 2 Dissolving in deionized water to obtain a solution containing metal ions C with the concentration of 1.8 mg/mL;
(2) Firstly, carrying out wet spinning by taking a polyelectrolyte solution X as a spinning solution, compounding for 20 hours by taking a polyelectrolyte solution Y as a coagulating bath, and then washing for 10 seconds to obtain a polyelectrolyte composite fiber; electrostatic force is formed between the skin layer and the core layer, the core layer is chitosan, and the skin layer is a mixture composed of sodium alginate and N, N-dicarboxymethylpolyallylamine with the mass ratio of 1; the mass ratio of the skin layer to the core layer is 1;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 8 hours, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 85% and still maintaining the skin-core structure;
in the prepared polyelectrolyte composite hydrogel fiber, carboxylate in the mixture forming the skin layer and polyvalent metal ion C form a coordination crosslinking structure, and the mixture and the polyvalent metal ion C (Zn) 2+ ) The mass ratio of (1).
The performance of the polyelectrolyte complex hydrogel fiber is tested as follows: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 135%, the monofilament strength is 20MPa, the initial modulus is 20MPa, and a weight which is 2 thousand times of the self weight can be pulled.
Example B1
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving sodium alginate in deionized water, and performing centrifugal defoaming to obtain a polyelectrolyte solution X with the mass fraction of 1.5wt.% of polyelectrolyte;
polyelectrolyte solution Y: dissolving chitosan in an acetic acid solution, adjusting the pH value of the solution to 3.5, and performing centrifugal deaeration to obtain a polyelectrolyte solution Y with the mass fraction of polyelectrolyte of 0.5 wt.%;
solution containing metal ion C: adding CaCl 2 Dissolving in deionized water to obtain a solution containing metal ions C with the concentration of 1 mg/mL;
(2) Carrying out wet spinning by taking a polyelectrolyte solution X as a spinning solution, compounding for 24 hours by taking a polyelectrolyte solution Y as a coagulating bath, and then washing for 20 seconds to obtain a polyelectrolyte composite fiber with a skin-core structure; wherein the skin layer is chitosan, the core layer is sodium alginate, and electrostatic force is formed between the skin layer and the core layer; the mass ratio of the skin layer to the core layer is 1;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 1h, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 72% and still maintaining the skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, carboxylate radicals in sodium alginate and polyvalent metal ions C form a coordination crosslinking structure, and the sodium alginate and the polyvalent metal ions C (Ca) 2+ ) The mass ratio of (2).
The performance of the polyelectrolyte complex hydrogel fiber is tested as follows: completely soaking the polyelectrolyte complex hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days to obtain: the elongation at break is 110%, the monofilament strength is 28MPa, the initial modulus is 89MPa, and a weight 1 ten thousand times of the self weight can be pulled.
Example B2
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving N, N-dicarboxymethylpolyallylamine in deionized water, adjusting the pH value to 3.5, and performing centrifugal defoaming to obtain a polyelectrolyte solution X with the mass fraction of polyelectrolyte of 0.8 wt%;
polyelectrolyte solution Y: dissolving polyallylamine in deionized water, adjusting the pH value to 3.5, and performing centrifugal defoaming to obtain a polyelectrolyte solution Y with the mass fraction of polyelectrolyte of 0.5 wt.%;
solution containing metal ion C: feCl is added 3 Dissolving in deionized water to obtain a solution containing metal ion C with the concentration of 1.5 mg/mL;
(2) Carrying out wet spinning by taking a polyelectrolyte solution X as a spinning solution, compounding for 18h by taking a polyelectrolyte solution Y as a coagulating bath, and then washing for 15s to obtain the polyelectrolyte composite fiber with a skin-core structure; wherein the skin layer is polyallylamine, the core layer is N, N-dicarboxymethyl polyallylamine, and electrostatic force is formed between the skin layer and the core layer; the mass ratio of the skin layer to the core layer is 1;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 2 hours, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with water content of 68% and still maintaining a skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, the carboxylate radical in the N, N-dicarboxymethyl polyallylamine and the polyvalent metal ion C form a coordination crosslinking structure, and the N, N-dicarboxymethyl polyallylamine and the polyvalent metal ion C (Fe) 3+ ) The mass ratio of (2).
The performance of the polyelectrolyte complex hydrogel fiber is tested as follows: completely soaking the polyelectrolyte complex hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days to obtain: the elongation at break is 80%, the monofilament strength is 40MPa, the initial modulus is 180MPa, and a weight 1 ten thousand times of the self weight can be pulled.
Example B3
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving N, N-dicarboxymethyl branched polyethyleneimine in deionized water, adjusting the pH value to 3, and performing centrifugal defoaming to obtain a polyelectrolyte solution X with the mass fraction of 0.8wt.% of polyelectrolyte;
polyelectrolyte solution Y: dissolving poly (diallyldimethylammonium chloride) in deionized water, adjusting the pH value of the solution to 3, and performing centrifugal deaeration to obtain a polyelectrolyte solution Y with the mass fraction of 0.8wt.% of polyelectrolyte;
solution containing metal ion C: mixing EuCl 3 Dissolving in deionized water to obtain a solution containing metal ions C with the concentration of 1 mg/mL;
(2) Carrying out wet spinning by taking a polyelectrolyte solution X as a spinning solution, compounding for 12 hours by taking a polyelectrolyte solution Y as a coagulating bath, and then washing for 25 seconds to obtain the polyelectrolyte composite fiber with a skin-core structure; wherein the skin layer is poly diallyl dimethyl ammonium chloride, the core layer is N, N-dicarboxymethyl branched polyethyleneimine, and electrostatic force is formed between the skin layer and the core layer; the mass ratio of the skin layer to the core layer is 2;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 5 hours, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 72% and still maintaining a skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, carboxylate radicals in N, N-dicarboxymethyl branched polyethyleneimine and polyvalent metal ions C form a coordination crosslinking structure, and the N, N-dicarboxymethyl branched polyethyleneimine and the polyvalent metal ions C (Eu) 3+ ) The mass ratio of (1).
The performance of the polyelectrolyte complex hydrogel fiber is tested as follows: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 95%, the monofilament strength is 35MPa, the initial modulus is 150MPa, and a weight 1 ten thousand times of the self weight can be pulled.
Example B4
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving N, N-dicarboxyl baseline polyethyleneimine in deionized water, adjusting the pH value to 3, and performing centrifugal defoaming to obtain a polyelectrolyte solution X with the mass fraction of 1.1wt.% of polyelectrolyte;
polyelectrolyte solution Y: dissolving polyallylamine and polydiallyldimethylammonium chloride in deionized water, adjusting the pH value to 3, and performing centrifugal deaeration to obtain a polyelectrolyte solution Y with the mass fraction of polyelectrolyte of 1 wt%;
solution containing metal ion C: adding CuCl 2 Dissolving in deionized water to obtain a solution containing metal ion C with the concentration of 1.2 mg/mL;
(2) Carrying out wet spinning by taking a polyelectrolyte solution X as a spinning solution, compounding for 24 hours by taking a polyelectrolyte solution Y as a coagulating bath, and then washing for 30 seconds to obtain a polyelectrolyte composite fiber with a skin-core structure; wherein the skin layer is polyallylamine and polydiallyldimethylammonium chloride, the core layer is N, N-dicarboxymethyl-based polyethyleneimine, and electrostatic force is formed between the skin layer and the core layer; the mass ratio of the skin layer to the core layer is 2;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 6 hours, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 78% and still maintaining the skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, carboxylate radicals in N, N-dicarboxyl-based polyethyleneimine and polyvalent metal ions C form a coordination crosslinking structure, and the N, N-dicarboxyl-based polyethyleneimine and the polyvalent metal ions C (Cu) 2+ ) 9.
The properties of the polyelectrolyte complex hydrogel fiber were tested as follows: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 120%, the monofilament strength is 10MPa, the initial modulus is 35MPa, and a heavy object with the weight 5 thousand times of the self weight can be pulled.
Example B5
A preparation method of a polyelectrolyte complex hydrogel fiber comprises the following specific steps:
(1) Preparing raw materials:
polyelectrolyte solution X: dissolving a mixture of N, N-dicarboxymethyl branched polyethyleneimine and N, N-dicarboxymethyl polyallylamine in a mass ratio of 1;
polyelectrolyte solution Y: dissolving chitosan in an acetic acid solution, adjusting the pH value of the solution to 3.5, and performing centrifugal defoaming to obtain a polyelectrolyte solution Y with the mass fraction of polyelectrolyte of 1 wt.%;
solution containing metal ion C: reacting ZnCl 2 Dissolving in deionized water to obtain a solution containing metal ion C with the concentration of 1.8 mg/mL;
(2) Carrying out wet spinning by taking a polyelectrolyte solution X as a spinning solution, compounding for 20 hours by taking a polyelectrolyte solution Y as a coagulating bath, and then washing for 10 seconds to obtain the polyelectrolyte composite fiber with a skin-core structure; wherein the skin layer is chitosan, the core layer is a mixture of N, N-dicarboxymethyl branched polyethyleneimine and N, N-dicarboxymethyl polyallylamine with the mass ratio of 1; the mass ratio of the skin layer to the core layer is 1;
(3) Completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment for 8 hours, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber with the water content of 88% and still maintaining the skin-core structure;
in the prepared polyelectrolyte complex hydrogel fiber, carboxylate in the mixture forming the core layer and polyvalent metal ion C form a coordination crosslinking structure, and the mixture and polyvalent metal ion C (Zn) 2+ ) 9.
The properties of the polyelectrolyte complex hydrogel fiber were tested as follows: completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 115%, the monofilament strength is 15MPa, the initial modulus is 50MPa, and a weight 6 thousand times of the self weight can be pulled.
Example B6
A method for preparing a polyelectrolyte complex hydrogel fiber, which comprises the following steps basically the same as those in example B5, except that a solution containing metal ions C is replaced by: ceCl 3 Dissolving in deionized water to obtain a solution; the prepared polyelectrolyte complex hydrogel fiber is completely immersed in deionized water, and the mechanical properties of the polyelectrolyte complex hydrogel fiber are tested after the polyelectrolyte complex hydrogel fiber is immersed for 2 days as follows: the elongation at break is 105%, the monofilament strength is 30MPa, the initial modulus is 80MPa, and a weight 1 ten thousand times of the self weight can be pulled.
Example B7
The preparation method of the polyelectrolyte complex hydrogel fiber comprises the following steps of: tbCl 3 Dissolving in deionized water to obtain a solution; will produceThe polyelectrolyte complex hydrogel fiber is completely immersed in deionized water, and the mechanical property of the polyelectrolyte complex hydrogel fiber is tested after the polyelectrolyte complex hydrogel fiber is immersed for 2 days as follows: the elongation at break is 100%, the monofilament strength is 35MPa, the initial modulus is 100MPa, and a weight 1 ten thousand times of the self weight can be pulled.
Claims (8)
1. A method for preparing polyelectrolyte complex hydrogel fiber is characterized in that: firstly, carrying out wet spinning by taking a polyelectrolyte solution X as a spinning solution, and compounding by a coagulating bath to obtain a polyelectrolyte composite fiber; completely immersing the polyelectrolyte composite fiber into a solution containing polyvalent metal ions C for treatment, and finally performing water absorption treatment to obtain the polyelectrolyte composite hydrogel fiber;
when the polyelectrolyte solution X is a solution with polycation electrolyte A as a solute, the solute of the polyelectrolyte solution Y as a coagulation bath is polyanion electrolyte B;
when the polyelectrolyte solution X is a solution with polyanionic electrolyte B as a solute, the solute of the polyelectrolyte solution Y serving as a coagulation bath is polycationic electrolyte A;
the mass fractions of the polyelectrolytes in the polyelectrolyte solution X and the polyelectrolyte in the polyelectrolyte solution Y are both 0.5 to 1.5wt.%;
the concentration of the solution containing the metal ions C is 1-2 mg/mL;
completely soaking the polyelectrolyte composite hydrogel fiber into deionized water, and testing the mechanical properties after soaking for 2 days: the elongation at break is 80-160%, the monofilament strength is 10-45 MPa, the initial modulus is 12-180 MPa, and a weight 2-1 ten thousand times of the self weight can be pulled.
2. The process according to claim 1, wherein the residence time of the dope in the coagulation bath after extrusion is 15min to 24h.
3. The method according to claim 1, wherein the polyelectrolyte complex fiber is treated for 24 hours or less by being completely immersed in the solution containing the polyvalent metal ion C.
4. The method according to claim 1, wherein the polyelectrolyte complex fiber is completely immersed in the solution containing the polyvalent metal ion C after being washed with water for 10 to 30 seconds.
5. A polyelectrolyte complex hydrogel fiber obtained by the method according to any one of claims 1 to 4, characterized in that: comprises polyelectrolyte composite fiber and polyvalent metal ion C therein;
the polyelectrolyte composite fiber has a skin-core structure, and electrostatic force is formed between the skin layer and the core layer; when the skin layer is the polycation electrolyte A, the core layer is the polyanion electrolyte B; when the core layer is the polycation electrolyte A, the skin layer is the polyanion electrolyte B;
carboxylate radicals in the polyanionic electrolyte B in the polyelectrolyte composite fiber and polyvalent metal ions C form a coordination crosslinking structure.
6. The polyelectrolyte complex hydrogel fiber as claimed in claim 5, wherein the mass ratio of the polyelectrolyte forming the skin layer to the polyelectrolyte forming the core layer is 1-2; the mass ratio of the polyanionic electrolyte B to the multivalent metal ions C is 8-12.
7. The polyelectrolyte complex hydrogel fiber according to claim 5, wherein the polycation electrolyte A is one or more of chitosan, polyallylamine and polydiallyldimethylammonium chloride; the polyanionic electrolyte B is more than one of sodium alginate, N-dicarboxymethyl polyallylamine, N-dicarboxymethyl branched polyethyleneimine and N, N-dicarboxymethyl baseline polyethyleneimine.
8. The polyelectrolyte complex hydrogel fiber according to claim 5, wherein the polyvalent metal ion C is Ca 2+ 、Fe 3+ 、Cu 2+ 、Zn 2+ 、Ce 3+ 、Eu 3+ Or Tb 3+ 。
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