CN114805694B - High-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and preparation method and application thereof - Google Patents

High-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and preparation method and application thereof Download PDF

Info

Publication number
CN114805694B
CN114805694B CN202110639724.0A CN202110639724A CN114805694B CN 114805694 B CN114805694 B CN 114805694B CN 202110639724 A CN202110639724 A CN 202110639724A CN 114805694 B CN114805694 B CN 114805694B
Authority
CN
China
Prior art keywords
acryloyl
hydrogel
carboxylic acid
strength
acid betaine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110639724.0A
Other languages
Chinese (zh)
Other versions
CN114805694A (en
Inventor
刘文广
范川川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University filed Critical Tianjin University
Priority to CN202110639724.0A priority Critical patent/CN114805694B/en
Publication of CN114805694A publication Critical patent/CN114805694A/en
Application granted granted Critical
Publication of CN114805694B publication Critical patent/CN114805694B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/52—Hydrogels or hydrocolloids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/06—Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Dermatology (AREA)
  • Public Health (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention provides a high-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and a preparation method and application thereof.A mixed solvent of dimethyl sulfoxide and deionized water is added into N-acryloyl carbamide and acryloyl carboxylic acid betaine for heating and dissolving to obtain a mixed solution, and a photoinitiator is added into the mixed solution for photoinitiated polymerization reaction to obtain a gel P; adding N-acryloyl carbamide and acryloyl carboxylic acid betaine into the gel P, heating and dissolving to obtain sol, adding a photoinitiator, and standing in an oven to remove bubbles to obtain bubble-free sol; carrying out photoinitiated polymerization on the sol, and soaking in water to obtain the lubricating copolymerization hydrogel with high rigidity, high strength and high toughness; or the bubble-free sol is transferred into a charging barrel of a 3D printer for 3D printing, and hydrogel supports with different shapes can be printed. According to the invention, the N-acryloyl carbamide monomer with higher concentration is added in a monomer post-compensation mode, so that the hydrogel has excellent mechanical properties.

Description

High-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and preparation method and application thereof
Technical Field
The invention relates to the technical field of lubricating hydrogel preparation, in particular to a lubricating copolymerization hydrogel with high rigidity, high strength and high toughness, and a preparation method and application thereof.
Background
Soft bearing tissues play an important role in the body, but their self-healing properties are poor when damaged due to the lack of vascular structure. The hydrogel as a water-rich material has good biocompatibility and has important application value in the aspect of soft tissue replacement.
In recent years, high-rigidity, high-strength and high-toughness hydrogel has been developed in a breakthrough manner, but due to the existence of contradiction between lubrication and strength, high-strength hydrogel hardly realizes good lubricity, and hydrogel with good lubricity often does not have excellent mechanical properties, because high-strength and high-rigidity require relative hydrophobicity of molecular chains, and lubricity requires hydrophilicity, so that the application of hydrogel in bearing tissues such as meniscus and the like is limited.
In previous work, a highly rigid hydrogel poly (N-acryloylcarbamide) (PNASC) hydrogel was prepared, but it was relatively hydrophobic, resulting in its higher friction factor. Acryloyl carboxylic acid betaine (CBAA) is taken as a super-hydrophilic monomer, and can form a hydration layer on the surface of hydrogel, thereby forming lubricity. But the lubricity requires the addition of a higher proportion of acryloyl carboxylic acid betaine (CBAA), thereby affecting the strength of the hydrogel.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides a high-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and a preparation method and application thereof, wherein a weak gel capable of being converted from gel/sol is obtained by copolymerization of low-concentration N-acryloyl carbamide (NASC) and acryloyl Carboxylic Betaine (CBAA), wherein the content of the acryloyl Carboxylic Betaine (CBAA) is relatively high, and the acryloyl Carboxylic Betaine (CBAA) endows the hydrogel with good lubricity, and then, a high-concentration N-acryloyl carbamide (NASC) monomer is added in a monomer post-compensation mode to endow the hydrogel with excellent mechanical properties, so that the method widens the way for preparation of the lubricating high-strength and high-rigidity hydrogel; and transferring the sol into a 3D printer cylinder for 3D printing.
The purpose of the invention is realized by the following technical scheme.
A high-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and a preparation method thereof are carried out according to the following steps:
step 1, N-Acrylureamide (NASC) and acryloyl carboxylic acid betaine (CBAA) were added to dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) to obtain a mixed solution, adding a photoinitiator into the mixed solution to carry out photoinitiated polymerization reaction to obtain gel P (NASC-CBAA), wherein the dosage ratio of N-acryloyl carbamide (NASC) to acryloyl carboxylic acid betaine (CBAA) is (20-50): (10-40) in a mixed solvent, dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) in a volume ratio of (2-4): (6-8);
step 2, adding N-acryloyl carbamide (NASC) and acryloyl carboxylic acid betaine (CBAA) into the gel P (NASC-CBAA) prepared in the step 1, heating and dissolving to obtain sol liquid, adding a photoinitiator into the sol liquid, standing in an oven to remove air bubbles to obtain the sol, wherein the dosage ratio of the N-acryloyl carbamide (NASC) to the acryloyl carboxylic acid betaine (CBAA) is (16-18): (2-4);
and 3, carrying out photoinitiated polymerization on the sol prepared in the step 2, and soaking in water to obtain the lubricating copolymer hydrogel with high rigidity, high strength and high toughness.
In step 1, N-acryloylurea amine (NASC) and acryloylcarboxylic betaine (CBAA) are used in a ratio of (30-40): (20-30) in a mixed solvent, dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) is 3:7.
In step 2, N-acryloylurea amine (NASC) and acryloylcarboxylic acid betaine (CBAA) were used in a ratio of 17:3.
in step 1 and step 2, irgacure 1173 is used as the photoinitiator.
In the step 1 and the step 3, the photoinitiated polymerization reaction time is 40-60min.
In step 1, the photoinitiator is used in an amount of 1-3% of the monomer concentration of N-acryloylurea amine (NASC) and acryloylcarboxylic acid betaine (CBAA), and in step 2, the photoinitiator is used in an amount of 1-3% of the monomer concentration of N-acryloylurea amine (NASC) and acryloylcarboxylic acid betaine (CBAA).
A method for 3D printing of a high-rigidity, high-strength and high-toughness lubricating copolymer hydrogel comprises the following steps:
step 1, adding N-acryloylurea amine (NASC) and acryloyl carboxylic acid betaine (CBAA) into a mixed solvent of dimethyl sulfoxide (DMSO) and deionized water (H2O), heating and dissolving to obtain a mixed solution, adding a photoinitiator into the mixed solution to perform photoinitiated polymerization reaction to obtain gel P (NASC-CBAA), wherein the mass ratio of the N-acryloylurea amine (NASC) to the acryloyl carboxylic acid betaine (CBAA) is (20-50): (10-40), in the mixed solvent, the volume ratio of dimethyl sulfoxide (DMSO) to deionized water (H2O) is (2-4): (6-8);
and 2, adding N-acryloyl carbamide (NASC) and acryloyl carboxylic acid betaine (CBAA) into the gel P (NASC-CBAA) prepared in the step 1, heating and dissolving to obtain sol liquid, adding a photoinitiator into the sol liquid, and standing in an oven to remove bubbles to obtain the sol, wherein the dosage ratio of the N-acryloyl carbamide (NASC) to the acryloyl carboxylic acid betaine (CBAA) is (16-18): (2-4);
step 3, adding the obtained sol obtained in the step 2 into a charging barrel of a 3D printer, and setting the printing temperature to be 40-50 ℃ to ensure that ink can be extruded, wherein the platform temperature is-10 to-2 ℃;
step 4, importing a printing model, and setting printing parameters: extrusion pressure of 8-12kPa and moving speed of 12-18mm s -1 Printing gel ink in a charging barrel of the 3D printer to obtain a 3D printing gel support;
and 5, carrying out ultraviolet light irradiation reaction on the 3D printing gel support obtained by printing in the step 2, soaking the 3D printing gel support in deionized water to complete solvent exchange after the reaction is finished, and storing in water.
In step 3, the printing temperature was 45 ℃ and the platen temperature was-5 ℃.
In step 4, the printing parameters: the extrusion pressure was 10kPa and the moving speed was 15mm s -1 。
The invention has the beneficial effects that: obtaining a weak gel capable of gel/sol transition by copolymerization of low-concentration N-acryloylurea amine (NASC) and acryloyl carboxylic acid betaine (CBAA), wherein the content of the acryloyl carboxylic acid betaine (CBAA) is relatively high, which endows hydrogel with good lubricity, and then adding a high-concentration N-acryloylurea amine (NASC) monomer in a monomer post-compensation manner to endow hydrogel with excellent mechanical properties, wherein the method widens the way for preparing the lubricating high-strength and high-rigidity hydrogel; the method is simple to operate, the obtained printing hydrogel has excellent mechanical property and lubricating property, the printed meniscus support can be implanted into a rabbit joint, the function reappearance of the meniscus of the rabbit is realized, and the application range of the printing hydrogel is widened for bearing tissue substitute materials
Drawings
FIG. 1 is a graph of the mechanical property test of the high-rigidity, high-strength and high-toughness lubricating copolymerized hydrogel prepared by the present invention, wherein a is a stress-strain curve of the PNASC-PCBAA copolymerized hydrogel, b is a graph of Young's modulus and strength data of the PNASC-PCBAA copolymerized hydrogel, c is a graph of toughness value of the PNASC-PCBAA copolymerized hydrogel, d is a graph of tearing energy value of the PNASC-PCBAA copolymerized hydrogel, e is a graph of comparison of the tearing energy and Young's modulus of the PNASC-PCBAA copolymerized hydrogel with other supramolecular hydrogels, and f is a graph of compressive stress-strain of the PNASC-PCBAA copolymerized hydrogel;
FIG. 2 is a friction performance diagram of the high-rigidity, high-strength and high-toughness lubricating copolymer hydrogel prepared by the invention, wherein a is a curve of the friction coefficient changing with time of hydrogels PNASC-30, PNASC-37.5-PCBAA-8.5, PNASC-PCBAA-6-40 and PNASC-46, b is a friction coefficient value diagram of the hydrogels PNASC-30, PNASC-37.5-PCBAA-8.5, PNASC-PCBAA-6-40 and PNASC-46, c is the cell adhesion condition of the hydrogel surface of the hydrogels PNASC-30, PNASC-37.5-PCBAA-8.5, PNASC-PCBAA-6-40 and PNASC-46;
FIG. 3 is a diagram of the rheological properties of the ink prepared by the present invention, wherein a is a curve of storage and loss moduli of the ink PNASC-PCBAA-6-40 varying with temperature, b is a shear-thinning curve of the ink PNASC-PCBAA-6-40, c is a graph of the viscosity of the ink PNASC-PCBAA-6-40 varying with strain rate, d is a graph of the viscosity of the ink PNASC-PCBAA-6-40 varying with strain rate in simulated printing, and e is a graph of the shear rate and temperature variation in simulated printing;
FIG. 4 is a photograph of different structures printed with inks prepared according to the present invention;
fig. 5 is a graph of mechanical properties and lubricating properties of the printed hydrogel prepared according to the present invention, where a is a tensile stress-strain curve of the printed PNASC-PCBAA-// hydrogel and the poured PNASC-PCBAA-6-40 hydrogel (PNASC-PCBAA-// hydrogel printed along the length direction), b is a tensile stress-strain curve of the printed PNASC-PCBAA-/-hydrogel and the poured PNASC-PCBAA-6-40 hydrogel (PNASC-PCBAA-/-hydrogel printed along the vertical length direction), c is a tear energy value graph of the printed PNASC-PCBAA hydrogel and the poured PNASC-PCBAA-6-40 hydrogel (PNASC-PCBAA-/-hydrogel printed along the vertical length direction), d is a tear energy value graph of the printed PNASC-PCBAA-/-hydrogel and the poured PNASC-PCBAA-6-40 hydrogel friction coefficient over time, and the printed PNASC-PCBAA hydrogel friction coefficient.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Step 1, 0.035g NASC and 0.025g CBAA were weighed into a centrifuge tube using an analytical balance, and a defined amount of dimethyl sulfoxide (DMSO) and deionized water (H) was added 2 O) (DMSO: 0.3mL; h 2 0.7 mL) to form a uniform solution, adding a certain amount of photoinitiator (1173.
Step 2, to the gel formed in step 1, a certain amount of NASC and CBAA (NASC: 0.17g CBAA.
And 3, pouring the sol formed in the step 2 into a mold, carrying out photoinitiated polymerization for 40-60min, and then soaking in water to obtain the high-strength, high-toughness and high-modulus lubricating hydrogel.
Example 2
Step 1, 0.035g NASC and 0.025g CBAA are weighed by an analytical balance and placed in a centrifuge tube, and a certain amount of dimethyl sulfoxide (DMSO) and deionized water (H) are added 2 O) (DMSO: 0.3mL; h 2 0.7 mL) to form a uniform solution, adding a certain amount of photoinitiator (1173.
Step 2, to the gel formed in step 1, a certain amount of NASC and CBAA (NASC: 0.34g CBAA.
And 3, pouring the sol formed in the step 2 into a mold, carrying out photoinitiated polymerization for 40-60min, and then soaking in water to obtain the high-strength, high-toughness and high-modulus lubricating hydrogel.
Example 3
Step 1, 0.035g NASC and 0.025g CBAA were weighed into a centrifuge tube using an analytical balance, and a defined amount of dimethyl sulfoxide (DMSO) and deionized water (H) was added 2 O) (DMSO: 0.3mL; h 2 0.7 mL) to form a uniform solution, adding a certain amount of photoinitiator (1173.
Step 2, to the gel formed in step 1, a certain amount of NASC and CBAA (NASC: 0.51g CBAA.
And 3, pouring the sol formed in the step 2 into a mold, carrying out photoinitiated polymerization for 40-60min, and then soaking in water to obtain the high-strength, high-toughness and high-modulus lubricating hydrogel.
The prepared hydrogel shows good mechanical property, as shown in figures 1a and b, the tensile strength and Young modulus of the hydrogel respectively reach 0.35-4.34MPa and 2.03-10.92MPa, and the hydrogel shows good toughness of 1.01-25.49MJ m -3 (FIG. 1 c), and a tear energy of up to 12.7kJ m -2 Beyond most supramolecular polymer hydrogels (fig. 1d, e), superior tear resistance was exhibited. In addition, as shown in figure 1f, the material has good compression performance, the compression strength can reach 3.8-22.01MPa, and the compression modulus can reach 0.66-6.56MPa.
In addition, the copolymerized hydrogel PNASC-PCBAA-6-x prepared by the two parts shows excellent lubricating performance, as shown in figures 2a and b, the friction coefficient of the copolymerized hydrogel can reach 0.06 and is obviously lower than that of other three hydrogels, and the value is remarkably lower than that (0.12) of the copolymerized hydrogel prepared by the one-step method, so that the copolymerized hydrogel prepared by the two-step method shows good lubricating performance. The good lubricity was also demonstrated by the adhesion test to cells (FIG. 2 c), in which the PNASC-PCBAA-6-40 hydrogel was less adherent to cells.
Example 4
Step 1, weigh separately a certain amount of NASC (0.035 g) and CBAA (0.025 g) using an analytical balance, then place it into a centrifuge tube, add 0.3mL of DMSO and 0.7mL of H 2 O, completely dissolving the mixture in a heating vortex mode, then adding a photoinitiator, uniformly mixing in a vortex mode, irradiating in ultraviolet crosslinking instrument for 40-60min to obtain P (NASC-CBAA) thermoreversible gel.
And 2, adding 0.34g of NASC and 0.06g of CBAA into the soft gel prepared in the step 1, heating the mixture to form uniform sol, adding a photoinitiator 1173 (4 mu L), and uniformly mixing by vortex to prepare the P (NASC-CBAA) + NASC + CBAA gel ink.
And 3, putting the gel ink prepared in the step 2 into a charging barrel of a 3D printer, setting the printing temperature to be 45 ℃, ensuring that the ink can be extruded, and setting the platform temperature to be-5 ℃.
Step 4, importing a printing model, and setting printing parameters (extrusion pressure 10kPa, moving speed 15mm s) -1 ) And printing the ink in the step 3.
And 5, carrying out ultraviolet irradiation on the gel support printed in the step 4 for 40-60min, soaking the gel support in deionized water to complete solvent exchange after the irradiation is finished, and storing the gel support in water.
The rheological properties of the ink PNASC-PCBAA-6-40 were tested, where it is shown in FIG. 3a that the storage and loss moduli of the ink gradually decreased with increasing temperature, and that the loss modulus G "exceeded the storage modulus G' around 45℃, indicating that the ink PNASC-PCBAA-6-40 started to transform from a gel state to a molten state, which transformation provides the possibility of being printable. Figure 3b shows that the ink gradually decreases in viscosity with increasing shear rate, which ensures continuous extrusion of the gel ink without clogging the jet. Fig. 3c shows the self-recovery of ink, which is important for fast shape fixing after ink printing. 3d, e shows that the hydrogel ink maintains a very high viscosity at room temperature and without shear, which gradually changes to a higher temperatureSol state, resulting in a viscosity reduction (while maintaining a low shear rate, first process I, i.e. a temperature rise process in the barrel); in the second process (II), the shearing rate is increased, the temperature is kept at 45 ℃, the viscosity of the gel ink is further reduced, which represents the extrusion process of printing and can ensure the smooth extrusion of the gel ink; the third process (III) restores the temperature and shear rate to the initial state (i.e., the ink deposition process after extrusion) and its viscosity returns to essentially the original value, indicating that it can be quickly fixed, ensuring high fidelity of the printed structure. Fig. 4 shows various shapes printed with gel ink, including (different size grids, menisci, music, snowflakes, and tree shapes). In the drawing tests of the printed hydrogels in different directions in fig. 5a and b, the tensile strength of the hydrogel parallel to the length direction can reach 1.87MPa, and the modulus can reach 10.98MPa, and in addition, as can be seen from fig. 5c to d, the printed hydrogel has higher compression strength (6.4 MPa) and higher tear energy (5333J m) -2 ) And good lubricity (COF,. About.0.05).
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. A high-rigidity, high-strength and high-toughness lubricating copolymer hydrogel is characterized in that: the method comprises the following steps:
step 1, adding N-acryloyl carbamide and acryloyl carboxylic acid betaine into a mixed solvent of dimethyl sulfoxide and deionized water, heating and dissolving to obtain a mixed solution, adding a photoinitiator into the mixed solution to perform photoinitiated polymerization reaction to obtain gel, wherein the mass ratio of the N-acryloyl carbamide to the acryloyl carboxylic acid betaine is (20-50): (10-40), in the mixed solvent, the volume ratio of the dimethyl sulfoxide to the deionized water is (2-4): (6-8);
step 2, adding N-acryloyl carbamide and acryloyl carboxylic acid betaine into the gel prepared in the step 1, heating and dissolving to obtain sol liquid, adding a photoinitiator into the sol liquid, and standing in an oven to remove bubbles to obtain sol, wherein the mass ratio of the N-acryloyl carbamide to the acryloyl carboxylic acid betaine is (16-18): (2-4);
and 3, carrying out photoinitiated polymerization on the sol prepared in the step 2, and soaking in water to obtain the lubricating copolymer hydrogel with high rigidity, high strength and high toughness.
2. A high stiffness, high strength, high toughness lubricating copolymeric hydrogel according to claim 1 wherein: in step 1, the mass ratio of the N-acryloyl urea amine to the acryloyl carboxylic acid betaine is (30-40): (20-30), in the mixed solvent, the volume ratio of the dimethyl sulfoxide to the deionized water is 3:7; in step 2, the ratio of the amount of N-acryloylurea amine to the amount of acryloyl carboxylic acid betaine is 17:3.
3. a high stiffness, high strength, high toughness lubricating copolymer hydrogel in accordance with claim 1 wherein: in the step 1 and the step 2, irgacure 1173 is adopted as the photoinitiator; in the step 1 and the step 3, the photoinitiated polymerization reaction time is 40-60min; in step 1, the photoinitiator is used in an amount of 1-3% of the concentration of the N-acryloylurea amine and acryloyl carboxylic acid betaine monomers, and in step 2, the photoinitiator is used in an amount of 1-3% of the concentration of the N-acryloylurea amine and acryloyl carboxylic acid betaine monomers.
4. A preparation method of a lubricating copolymer hydrogel with high rigidity, high strength and high toughness is characterized in that: the method comprises the following steps:
step 1, adding N-acryloyl carbamide and acryloyl carboxylic acid betaine into a mixed solvent of dimethyl sulfoxide and deionized water, heating and dissolving to obtain a mixed solution, adding a photoinitiator into the mixed solution to perform photoinitiated polymerization reaction to obtain gel, wherein the mass ratio of the N-acryloyl carbamide to the acryloyl carboxylic acid betaine is (20-50): (10-40), wherein the volume ratio of dimethyl sulfoxide to deionized water in the mixed solvent is (2-4): (6-8);
step 2, adding N-acryloyl carbamide and acryloyl carboxylic acid betaine into the gel prepared in the step 1, heating and dissolving to obtain sol liquid, adding a photoinitiator into the sol liquid, and standing in an oven to remove bubbles to obtain sol, wherein the dosage ratio of the N-acryloyl carbamide to the acryloyl carboxylic acid betaine is (16-18): (2-4);
and 3, carrying out photoinitiated polymerization on the sol prepared in the step 2, and soaking in water to obtain the lubricating copolymer hydrogel with high rigidity, high strength and high toughness.
5. The method for preparing a high-rigidity, high-strength, high-toughness lubricating copolymer hydrogel according to claim 4, wherein: in step 1, the ratio of the N-acryloyl urea amine to the acryloyl carboxylic acid betaine is (30-40): (20-30), in the mixed solvent, the volume ratio of the dimethyl sulfoxide to the deionized water is 3:7; in step 2, the ratio of the amount of N-acryloylurea amine to the amount of acryloyl carboxylic acid betaine is 17:3.
6. the method for preparing a high-rigidity, high-strength, high-toughness lubricating copolymer hydrogel according to claim 4, wherein: in the step 1 and the step 2, irgacure 1173 is adopted as the photoinitiator; in the step 1 and the step 3, the photoinitiated polymerization reaction time is 40-60min; in step 1, the photoinitiator is used in an amount of 1-3% of the concentration of the N-acryloylurea amine and acryloyl carboxylic acid betaine monomers, and in step 2, the photoinitiator is used in an amount of 1-3% of the concentration of the N-acryloylurea amine and acryloyl carboxylic acid betaine monomers.
7. A3D printing method of a high-rigidity, high-strength and high-toughness lubricating copolymer hydrogel is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding N-acryloyl carbamide and acryloyl carboxylic acid betaine into a mixed solvent of dimethyl sulfoxide and deionized water, heating and dissolving to obtain a mixed solution, adding a photoinitiator into the mixed solution to perform photoinitiated polymerization reaction to obtain gel, wherein the mass ratio of the N-acryloyl carbamide to the acryloyl carboxylic acid betaine is (20-50): (10-40), in the mixed solvent, the volume ratio of the dimethyl sulfoxide to the deionized water is (2-4): (6-8);
step 2, adding N-acryloyl carbamide and acryloyl carboxylic acid betaine into the gel prepared in the step 1, heating and dissolving to obtain sol liquid, adding a photoinitiator into the sol liquid, and standing in an oven to remove bubbles to obtain sol, wherein the dosage ratio of the N-acryloyl carbamide to the acryloyl carboxylic acid betaine is (16-18): (2-4);
step 3, adding the obtained sol obtained in the step 2 into a charging barrel of a 3D printer, setting the printing temperature to be 40-50 ℃ to ensure that ink can be extruded, and setting the platform temperature to be-10-2 ℃;
step 4, importing a printing model, and setting printing parameters: the extrusion pressure is 8-12kPa, and the moving speed is 12-18mm s -1 Printing gel ink in a charging barrel of the 3D printer to obtain a 3D printing gel support;
and 5, carrying out ultraviolet light irradiation reaction on the 3D printing gel support obtained by printing in the step 2, soaking the 3D printing gel support in deionized water to complete solvent exchange after the reaction is finished, and storing in water.
8. The method for 3D printing of a high stiffness, high strength, high toughness lubricating copolymeric hydrogel of claim 7 wherein: in step 3, the printing temperature is 45 ℃ and the platform temperature is-5 ℃; in step 4, the printing parameters: the extrusion pressure was 10kPa and the moving speed was 15mm s -1 。
9. Use of a high rigidity, high strength, high toughness lubricious copolymeric hydrogel of any of claims 1-3 in a soft tissue replacement material.
10. Use according to claim 9, characterized in thatThe method comprises the following steps: the high-rigidity, high-strength and high-toughness lubricating copolymerized hydrogel has tensile strength of 0.35-4.34MPa, young's modulus of 2.03-10.92MPa and toughness of 1.01-25.49MJ m -3 The tear energy of the lubricating copolymerized hydrogel with high rigidity, high strength and high toughness is 12.0-13.0kJm -2 The lubricating copolymer hydrogel has the tearing resistance, the compressive strength of the lubricating copolymer hydrogel with high rigidity, high strength and high toughness is 3.8-22.01MPa, the compressive modulus of the lubricating copolymer hydrogel with high rigidity, high strength and high toughness is 0.66-6.56MPa, and the friction coefficient of the lubricating copolymer hydrogel with high rigidity, high strength and high toughness is 0.05-0.07; the tensile strength of the printed hydrogel is 0.8-2MPa, the Young modulus of the printed hydrogel is 8-12MPa, the compressive strength of the printed hydrogel is 5-7MPa, the compressive modulus is 0.1-0.2MPa, and the tearing energy of the printed hydrogel is 4500-6000Jm -2 The coefficient of friction of the hydrogel after printing was between 0.045 and 0.07.
CN202110639724.0A 2021-06-08 2021-06-08 High-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and preparation method and application thereof Active CN114805694B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110639724.0A CN114805694B (en) 2021-06-08 2021-06-08 High-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110639724.0A CN114805694B (en) 2021-06-08 2021-06-08 High-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114805694A CN114805694A (en) 2022-07-29
CN114805694B true CN114805694B (en) 2023-03-28

Family

ID=82525684

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110639724.0A Active CN114805694B (en) 2021-06-08 2021-06-08 High-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114805694B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114106227B (en) * 2021-12-23 2022-09-16 中国科学院兰州化学物理研究所 Preparation method of structured hydrogel and hydrogel heart and valve
CN116196480B (en) * 2023-02-24 2024-05-24 天津大学 3D printing hydrogen bond crosslinking supermolecular polymer high-strength hydrogel-based meniscus scaffold and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110857326B (en) * 2018-08-22 2021-09-07 天津大学 Supermolecule polymer hydrogel with injectability and rapid recovery performance as well as preparation method and application thereof
CN112521550A (en) * 2019-09-18 2021-03-19 天津大学 Supermolecule copolymerized hydrogel and preparation method thereof
CN112521625A (en) * 2019-09-18 2021-03-19 天津大学 High-modulus supramolecular polymer hydrogel based on carbamide and preparation method thereof

Also Published As

Publication number Publication date
CN114805694A (en) 2022-07-29

Similar Documents

Publication Publication Date Title
CN114805694B (en) High-rigidity, high-strength and high-toughness lubricating copolymer hydrogel and preparation method and application thereof
Dávila et al. Rheological evaluation of Laponite/alginate inks for 3D extrusion-based printing
Dizon et al. Thermo-mechanical and swelling properties of three-dimensional-printed poly (ethylene glycol) diacrylate/silica nanocomposites
Yao et al. An unparalleled H-bonding and ion-bonding crosslinked waterborne polyurethane with super toughness and unprecedented fracture energy
CN104262881B (en) A kind of preparation method of high intensity dual network nano silicon composite aquogel
EP2598304B1 (en) In-mould-foaming process using a foamable medium with outer layers, and plastics moulding obtainable therefrom
Bakarich et al. 3D/4D printing hydrogel composites: a pathway to functional devices
CN108276522A (en) Can 3D printing the double cross-linked alginate-polyacrylamide acrylic acid high-performance water gels of iron ion preparation method
CN114316685B (en) Ink direct-writing 3D printing PEDOT/PSS composite hydrogel and preparation method thereof
CN112480312B (en) Preparation method of high-elasticity high-strength double-crosslinking porous hydrogel
CN110256715B (en) Small-aperture polymethacrylimide foam and preparation method thereof
CN109880305A (en) A kind of method of hydrogel-elastomer composite 3D printing
US20230201427A1 (en) Method for preparing structured hydrogel and method for preparing hydrogel heart valve
Pan et al. Optical stereolithography of antifouling zwitterionic hydrogels
CN109603568B (en) Preparation method of high-strength three-network porous hydrogel oil-water separation membrane
Lin et al. Nonswellable hydrogels with robust micro/nano-structures and durable superoleophobic surfaces under seawater
Xiang et al. 3D-printed high-toughness double network hydrogels via digital light processing
CN103333311A (en) Fluorinated carbon nano-tube/thermoplastic fluorine-containing polyurethane composite elastomer and preparation method thereof
CN109467642A (en) High-strength temperature-sensitive supramolecular hydrogel capable of being printed in 3D mode and preparation method thereof
CN101480501B (en) Substitute material for repairing articular cartilage and preparation method
CN107759732A (en) Methyl propane sulfonic acid copolymer hydrogel of acryloyl group glycine amide/2 acrylamide 2 and preparation method thereof
CN106589731A (en) Method for preparing IPN structure PMMA-PU high-transparency composite board through ultrasonic assistance
CN112755244A (en) Hydrophilic polymer hydrogel stent and preparation method thereof
CN115490980B (en) Gel rate adjustable 3D printing hydrogel ink
CN107759733A (en) Application based on the supermolecule composite aquogel of acryloyl group glycine amide in 3D printing

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant