CN112940180B - PHEAA-based high-toughness hydrogel and preparation method and application thereof - Google Patents

PHEAA-based high-toughness hydrogel and preparation method and application thereof Download PDF

Info

Publication number
CN112940180B
CN112940180B CN202110084508.4A CN202110084508A CN112940180B CN 112940180 B CN112940180 B CN 112940180B CN 202110084508 A CN202110084508 A CN 202110084508A CN 112940180 B CN112940180 B CN 112940180B
Authority
CN
China
Prior art keywords
hydrogel
toughness
acrylamide
hydroxyethyl
photoinitiator
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
CN202110084508.4A
Other languages
Chinese (zh)
Other versions
CN112940180A (en
Inventor
王�义
赵丽娟
吴锦荣
宋永娇
易龙飞
刘勇
伍俊良
欧阳宏妍
谢袁杰
罗星琪
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.)
Sichuan University
West China Hospital of Sichuan University
Sichuan Normal University
Original Assignee
Sichuan University
West China Hospital of Sichuan University
Sichuan Normal 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 Sichuan University, West China Hospital of Sichuan University, Sichuan Normal University filed Critical Sichuan University
Priority to CN202110084508.4A priority Critical patent/CN112940180B/en
Publication of CN112940180A publication Critical patent/CN112940180A/en
Application granted granted Critical
Publication of CN112940180B publication Critical patent/CN112940180B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/16Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/52Hydrogels or hydrocolloids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04Anhydrides, e.g. cyclic anhydrides
    • C08F222/06Maleic anhydride
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/06Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/10Materials or treatment for tissue regeneration for reconstruction of tendons or ligaments

Abstract

The invention provides PHEAA-based high-toughness hydrogel and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The hydrogel has a structure shown in a formula I, wherein x is 100-300; y is 20-50; z is 50-300. The invention uses N- (2-hydroxyethyl) acrylamide (HEAA) to copolymerize with maleic anhydride to obtain the hydrogel with uniform network structure, and the hydrogel has high fracture toughness and good biocompatibility. The hydrogel can overcome the defects of the existing cartilage, achilles tendon and other tissue repair materials due to excellent mechanical properties and biocompatibility, and the tissue repair material with better preparation performance is expected to be widely applied to the aspects of artificial cartilage, artificial achilles tendon and the like, and has good application prospect.
Figure DDA0002910292110000011

Description

PHEAA-based high-toughness hydrogel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to PHEAA-based high-toughness hydrogel, and a preparation method and application thereof.
Background
The articular cartilage defect is caused by diseases such as wound, inflammation, tumor and the like, and is a relatively common clinical lesion. The method is superior to the method that the blood supply in cartilage is limited, so that the self-repairing capability of cartilage tissues is poor, and large-area cartilage damage (> 4 mm) cannot be repaired by self, because cartilage defects are one of the problems of great concern in the medical field. At present, cartilage tissue repair is mainly carried out by methods such as cartilage inhibition, chondrocyte transplantation or periosteum transplantation, and although a certain curative effect is achieved, the method is limited in that good integration of a graft and self cartilage tissue cannot be achieved in a clinical repair process, so that the treatment effect is poor. In recent years, the application of artificial cartilage scaffold materials for repairing cartilage defects in orthopaedics is becoming wider and wider. Gel materials that are structurally and functionally similar to articular cartilage are considered as a promising articular cartilage repair material.
The hydrogel material has the potential advantages as a cartilage tissue engineering scaffold material that: high moisture content, low friction coefficient, etc. However, most hydrogel materials contain more than 80% moisture, and despite their high flexibility, have poor mechanical properties such as low fracture toughness, low fracture strain, and low strength. In addition, since the cross-linking points of the hydrogel tend to be randomly incorporated into the network structure during gelation, non-uniformity of the gel network structure is caused. When the gel with uneven network is deformed, the gel can be broken from the weakest link, so that the overall mechanical property of the gel is reduced. The weaker mechanical properties make it difficult for the hydrogel to withstand significant mechanical loads and accommodate a greater degree of deformation. At present, the material mainly used for cartilage repair is polyvinyl alcohol (PVA), the mechanical property of the PVA is very similar to that of articular cartilage, the PVA has good biocompatibility, and the PVA hydrogel can possibly partially replace the articular cartilage after being implanted into a human body, but when the PVA hydrogel is singly used for replacing diseased cartilage tissues, the mechanical strength of the PVA hydrogel cannot meet the requirements of real cartilage tissues.
In order to improve the mechanical properties of hydrogels, various chemical additives are often required to be added, and most of the additives are harmful to human bodies, resulting in reduced biocompatibility of hydrogels. Therefore, the mechanical property and the biocompatibility of the hydrogel are often difficult to be simultaneously considered, so that the application of the hydrogel material in the fields of artificial cartilage, artificial achilles tendon and the like is hindered. Therefore, from the network structure design of the hydrogel, a new design principle is proposed, and nontoxic raw materials are selected to prepare the hydrogel material with high toughness and biocompatibility, so that the hydrogel material is suitable for the aspects of artificial cartilage, artificial achilles tendon and the like.
Poly N- (2-hydroxyethyl) acrylamide (PHEAA) is an electrically neutral polymer with good biocompatibility and thermal stability, and researches show that PHEAA has the function of resisting nonspecific protein adsorption. Zhao et al (C.zhao et al, dual Functionality of Antimicrobial and Antifouling of Poly (N-hydroxymethylacrylamide)/Salicylate Hydrogels [ J ]. Langmuir,2013,29 (5): 1517-1524.) synthesized a PHEAA/salicylic acid hydrogel that was both anti-fouling and anti-bacterial, and was found to have high resistance to protein adsorption, bacteria, and cell adhesion.
However, no hydrogel with good biocompatibility and high toughness is obtained by copolymerization of PHEAA and Maleic Anhydride (MA).
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and provides a hydrogel with high toughness and excellent biocompatibility, which is prepared by copolymerizing N- (2-hydroxyethyl) acrylamide (HEAA) and Maleic Anhydride (MA), and can be used as a repair material for tissues such as cartilage, achilles tendon and the like.
The invention provides a PHEAA-based high-toughness hydrogel, which has a structure shown in a formula I:
Figure BDA0002910292090000021
wherein, the liquid crystal display device comprises a liquid crystal display device,
x is 100-300; y is 20-50; z is 50-300.
Further, the hydrogel is prepared from N- (2-hydroxyethyl) acrylamide and acid or anhydride containing C=C unsaturated bonds as raw materials; wherein the molar ratio of the N- (2-hydroxyethyl) acrylamide to the acid or anhydride containing C=C unsaturated bond is 8: (1-8).
Further, the molar ratio of the N- (2-hydroxyethyl) acrylamide to the acid or anhydride containing the C=C unsaturated bond is 8: (2-3).
Further, the acid or anhydride containing c=c unsaturated bond is maleic anhydride.
Further, the fracture toughness of the hydrogel is not lower than 1MJ/m 3
The hydrogels of the present invention are obtained by copolymerizing N- (2-hydroxyethyl) acrylamide and an acid or anhydride containing a c=c unsaturated bond.
Preferably, the hydrogel is obtained by copolymerizing N- (2-hydroxyethyl) acrylamide and an acid or anhydride containing a c=c unsaturated bond after uv irradiation in the presence of a photoinitiator.
The invention also provides a method for preparing the high-toughness hydrogel, which comprises the following steps:
a. dissolving N- (2-hydroxyethyl) acrylamide and an acid or anhydride containing a c=c unsaturated bond in water;
b. adding a photoinitiator;
c. irradiating with ultraviolet light to obtain the final product.
Further, the oxygen in the system is removed before the photoinitiator is added in the step b.
Preferably, the oxygen in the removing system is removed by introducing inert gas.
More preferably, the inert gas is nitrogen, and the time for introducing the nitrogen is 1-60 min.
Further, the molar ratio of the photoinitiator to the N- (2-hydroxyethyl) acrylamide in the step b is (0.0001-0.024): 8, 8; preferably, the molar ratio of the photoinitiator to the N- (2-hydroxyethyl) acrylamide is (0.001-0.003): 8, 8; the photoinitiator is 2-hydroxy-2-methyl propiophenone or benzoin dimethyl ether.
Further, the ultraviolet irradiation conditions in the step c are as follows: the wavelength of the ultraviolet light is 10-400 nm; and/or the irradiation power of the ultraviolet light is 10-400W; and/or the ultraviolet irradiation time is 10-120 min.
Preferably, the ultraviolet light wavelength is 300-380 nm; and/or the irradiation power of the ultraviolet light is 300-360W.
More preferably, the ultraviolet light wavelength is 365nm; and/or the irradiation power of the ultraviolet light is 330W; and/or the ultraviolet irradiation time is 40-120 min.
The invention also provides application of the high-toughness hydrogel in preparing a tissue repair material.
Preferably, the high-toughness hydrogel is used for preparing cartilage repair materials and Achilles tendon repair materials.
More preferably, the high toughness hydrogel is used for preparing artificial cartilage and artificial achilles tendon.
The mechanical properties and biocompatibility of hydrogels are difficult to be compatible at the same time, resulting in limited applications in artificial cartilage, artificial achilles tendon, and the like. There is a need to improve the toughness of PHEAA while ensuring good biocompatibility to prepare high-toughness and good-biocompatibility hydrogel. The invention provides a technical scheme for preparing PHEAA-based hydrogel with high toughness and good biocompatibility.
The hydrogel is prepared by reacting HEAA and maleic anhydride under the photoinitiation effect for 10-120 min. Wherein, the photoinitiator is benzoin dimethyl ether (Irgacure-651) or 2-hydroxy-2-methyl propiophenone (1173), and the light source is ultraviolet light with the wavelength of 10-400 nm, preferably 300-380 nm and the power of 10-400W, preferably 300-360W. The irradiation power of the ultraviolet light is not too high, otherwise, excessive heat can cause thermal initiation of free radical polymerization, thereby affecting the performance of the hydrogel.
Compared with the prior art, the invention has the following outstanding advantages and technical effects:
the PHEAA-based hydrogel prepared by the invention has a uniform network structure, and is different from the traditional PHEAA hydrogel in that the breakage of short chains is easy to occur due to the fact that the chain length of molecules is different; and, through the carboxyl of maleic anhydride and hydroxyl and amino in HEAA form the strong hydrogen bond to act; hydrogen bonding between amino-amino, amino-hydroxy, hydroxy-hydroxy can also be formed within the HEAA structural unit. Therefore, the hydrogel can generate affine deformation through a uniform network at the initial stage of deformation, so that breakage caused by the existence of stress concentration is avoided; with further increase of deformation, the breaking of hydrogen bonding can effectively dissipate energy, and the toughness of the hydrogel is remarkably improved. Therefore, the PHEAA-based hydrogel prepared by adopting HEAA and maleic anhydride through photoinitiated free radical copolymerization has the advantage of high toughness, and meanwhile, the PHEAA-based hydrogel is harmless to human bodies and good in biocompatibility, and is expected to be widely applied to the aspects of artificial cartilage, artificial achilles tendon and the like.
In summary, the present invention uses N- (2-hydroxyethyl) acrylamide (HEAA) copolymerized with maleic anhydride to obtain hydrogels with uniform network structure, which have high fracture toughness and good biocompatibility. The hydrogel can overcome the defects of the existing cartilage, achilles tendon and other tissue repair materials due to excellent mechanical properties and biocompatibility, and the tissue repair material with better preparation performance is expected to be widely applied to the aspects of artificial cartilage, artificial achilles tendon and the like, and has good application prospect.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is a graph of time-averaged scattering intensity for different hydrogel samples<I> T The amplitude of the fluctuation varies with the position of the sample.
Detailed Description
The materials and equipment used in the embodiments of the present invention are all known products and are obtained by purchasing commercially available products.
The synthetic route of the hydrogel of the invention is as follows:
Figure BDA0002910292090000041
wherein, the liquid crystal display device comprises a liquid crystal display device,
x is 100-300; y is 20-50; z is 50-300.
EXAMPLE 1 preparation of hydrogels of the invention
N- (2-hydroxyethyl) acrylamide (HEAA) and Maleic Anhydride (MA) with the molar ratio of 8:1 are dissolved in water, namely 8mol HEAA and 1mol MA are dissolved in 50mL of water, nitrogen is introduced into the solution for 10min under stirring to remove oxygen in the solution, and then 0.003mol of photoinitiator benzoin dimethyl ether (Irgacure-651) is added, and the mixture is subjected to illumination reaction for 40min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W, so that P (HEAA-co-MA) hydrogel A is obtained.
EXAMPLE 2 preparation of hydrogels of the invention
N- (2-hydroxyethyl) acrylamide (HEAA) and Maleic Anhydride (MA) with the molar ratio of 8:2 are dissolved in water, namely 8mol HEAA and 2mol MA are dissolved in 50mL of water, nitrogen is introduced into the solution for 20min under stirring to remove oxygen in the solution, and then 0.003mol of photoinitiator benzoin dimethyl ether (Irgacure-651) is added, and the mixture is subjected to illumination reaction for 40min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W, so that P (HEAA-co-MA) hydrogel B is obtained.
Example 3 preparation of hydrogels of the invention
N- (2-hydroxyethyl) acrylamide (HEAA) and Maleic Anhydride (MA) with the molar ratio of 12:5 are dissolved in water, namely 12mol of HEAA and 5mol of MA are dissolved in 50mL of water, nitrogen is introduced into the solution for 60min under stirring to remove oxygen in the solution, and then 0.003mol of photoinitiator benzoin dimethyl ether (Irgacure-651) is added, and the mixture is subjected to illumination reaction for 40min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W, so that P (HEAA-co-MA) hydrogel C is obtained.
EXAMPLE 4 preparation of hydrogels of the invention
N- (2-hydroxyethyl) acrylamide (HEAA) and Maleic Anhydride (MA) with a molar ratio of 8:3 are dissolved in water, namely 8mol HEAA and 3mol MA are dissolved in 50mL of water, nitrogen is introduced into the solution for 1min under stirring to remove oxygen in the solution, and then 0.001mol of a photoinitiator benzoin dimethyl ether (Irgacure-651) is added to react for 120min under the irradiation of an ultraviolet lamp with a wavelength of 10nm and a power of 10W, so that P (HEAA-co-MA) hydrogel D is obtained.
EXAMPLE 5 preparation of hydrogels of the invention
N- (2-hydroxyethyl) acrylamide (HEAA) and Maleic Anhydride (MA) with the molar ratio of 1:1 are dissolved in water, namely 1mol HEAA and 1mol MA are dissolved in 50mL of water, nitrogen is introduced into the solution for 10min under stirring to remove oxygen in the solution, and then 0.003mol of photoinitiator benzoin dimethyl ether (Irgacure-651) is added to carry out illumination reaction for 10min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W, so that P (HEAA-co-MA) hydrogel E is obtained.
EXAMPLE 6 preparation of hydrogels of the invention
N- (2-hydroxyethyl) acrylamide (HEAA) and Maleic Anhydride (MA) with the molar ratio of 8:3 are dissolved in water, namely 8mol HEAA and 3mol MA are dissolved in 50mL of water, nitrogen is introduced into the solution for 10min under stirring to remove oxygen in the solution, and then 0.003mol of photoinitiator benzoin dimethyl ether (Irgacure-651) is added, and the mixture is subjected to illumination reaction for 60min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W, so that P (HEAA-co-MA) hydrogel F is obtained.
Comparative example 1 preparation of PHEAA hydrogel
N- (2-hydroxyethyl) acrylamide (HEAA) and Maleic Anhydride (MA) with the molar ratio of 8:0 are dissolved in water, namely 8mol HEAA is dissolved in 50mL of water, nitrogen is introduced into the solution for 10min under stirring to remove oxygen in the solution, then 0.003mol of photoinitiator benzoin dimethyl ether (Irgacure-651) is added, and the mixture is subjected to illumination reaction for 40min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W, so that the PHEAA hydrogel is obtained.
The beneficial effects of the present invention are demonstrated by specific test examples below.
Test example 1 Performance test of hydrogels of the invention
(1) Mechanical property test: the tensile stress-strain behavior of each set of hydrogels (examples 1-6 and comparative example 1) was evaluated separately using a universal tensile tester Instron 3367 at a tensile rate of 100mm/min, the samples were stretched until fracture, and stress-strain curves were recorded. Wherein fracture toughness is determined by the integrated area under the corresponding stress-strain curve at which the sample breaks. The hydrogel sample is dumbbell-shaped, and has a gauge length of 10mm, a width of 4mm and a thickness of 1mm.
(2) Cell compatibility test: the hydrogels prepared in examples 1 to 6 and comparative example 1 were cut into discs of 2.5mm diameter and 1mm thickness, and the surface was inoculated with mesenchymal stem cells of the same density at 37℃and cultured for 24 hours, and then the cell activity was evaluated using CCK-8 assay.
(3) Uniformity test (dynamic light scattering test): characterization of time-averaged Scattering Strength at different sample positions for each set of hydrogels (examples 1-6 and comparative example 1) using BI-200SM measurement System<I> T Is a fluctuation amplitude of (a). The time-averaged scattered intensity refers to the average scattered light intensity over a certain time.
The mechanical properties and the cell compatibility test results of the hydrogels of the present invention are shown in table 1.
TABLE 1 mechanical Properties and cell compatibility test results of hydrogels of the invention
Figure BDA0002910292090000061
As can be seen from table 1: with PHEAA hydrogelCompared with the MA, the fracture toughness of the hydrogel after copolymerization is obviously improved from 0.12MJ/m 3 The temperature is increased to 1.36-2.36 MJ/m 3 The mechanical requirement of the material serving as a tissue repair material of cartilage, achilles tendon and the like can be met. Meanwhile, from the cell culture experiment, after the mesenchymal stem cells are cultured on each group of hydrogel for 24 hours, the cell survival rate is as high as 85-95%, which indicates that the hydrogel has excellent biocompatibility. Comprehensively, the hydrogel B, C, D has the best performance.
The variation of the non-uniformity of the hydrogel network can be analyzed by dynamic light scattering test, and the time average scattering intensity<I> T The more pronounced the fluctuations of (c) indicate a more heterogeneous hydrogel structure. Time-averaged scatter intensity for each set of hydrogels<I> T The fluctuation amplitude of (2) is shown in FIG. 1. The results show that: time-averaged scattering intensity of PHEAA hydrogels<I> T Fluctuation ratio of hydrogel A-F time-averaged scattering intensity<I>The fluctuation of T was more pronounced and severe, indicating that the structure of hydrogels A-F was more uniform than that of PHEAA hydrogels. The more uniform network structure enables the hydrogel to bear larger mechanical load and adapt to larger deformation, thereby improving the overall mechanical property of the hydrogel and being more suitable for serving as repair materials of cartilage, achilles tendon and the like.
In summary, the present invention uses N- (2-hydroxyethyl) acrylamide (HEAA) copolymerized with maleic anhydride to obtain hydrogels with uniform network structure, which have high fracture toughness and good biocompatibility. The hydrogel can overcome the defects of the existing cartilage, achilles tendon and other tissue repair materials due to excellent mechanical properties and biocompatibility, and the tissue repair material with better preparation performance is expected to be widely applied to the aspects of artificial cartilage, artificial achilles tendon and the like, and has good application prospect.

Claims (11)

1. A high-toughness hydrogel based on PHEAA, characterized in that: the structure of the hydrogel is shown as formula I:
Figure QLYQS_1
i is a kind of
Wherein, the liquid crystal display device comprises a liquid crystal display device,
x is 100-300; y is 20-50; z is 50-300.
2. The high toughness hydrogel according to claim 1, wherein: the hydrogel is prepared from N- (2-hydroxyethyl) acrylamide and acid or anhydride containing C=C unsaturated bonds as raw materials; wherein the molar ratio of the N- (2-hydroxyethyl) acrylamide to the acid or anhydride containing C=C unsaturated bond is 8: (1-8).
3. The high-toughness hydrogel according to claim 2, wherein: the molar ratio of the N- (2-hydroxyethyl) acrylamide to the acid or anhydride containing the C=C unsaturated bond is 8: (2-3).
4. The high-toughness hydrogel according to claim 3, wherein: the acid or anhydride containing C=C unsaturated bond is maleic anhydride.
5. The high-toughness hydrogel according to any one of claims 1 to 4, wherein: the fracture toughness of the hydrogel is not less than 1MJ/m 3
6. A method for preparing the high-toughness hydrogel according to any one of claims 1 to 5, characterized in that: it comprises the following steps:
a. dissolving N- (2-hydroxyethyl) acrylamide and an acid or anhydride containing a c=c unsaturated bond in water;
b. adding a photoinitiator;
c. irradiating with ultraviolet light to obtain the final product.
7. The method according to claim 6, wherein: and b, removing oxygen in the system before adding the photoinitiator.
8. The method according to claim 6, wherein: the molar ratio of the photoinitiator to the N- (2-hydroxyethyl) acrylamide in the step b is (0.0001-0.024): 8.
9. the method according to claim 8, wherein: the molar ratio of the photoinitiator to the N- (2-hydroxyethyl) acrylamide in the step b is (0.001-0.003): 8, 8; the photoinitiator is 2-hydroxy-2-methyl propiophenone or benzoin dimethyl ether.
10. The method according to claim 6, wherein: the ultraviolet irradiation conditions in the step c are as follows: the ultraviolet light wavelength is 10-400 nm; and/or the irradiation power of the ultraviolet light is 10-400W; and/or the ultraviolet irradiation time is 10-120 min.
11. The use of the high-toughness hydrogel according to any one of claims 1 to 5 for preparing a tissue repair material.
CN202110084508.4A 2021-01-21 2021-01-21 PHEAA-based high-toughness hydrogel and preparation method and application thereof Active CN112940180B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110084508.4A CN112940180B (en) 2021-01-21 2021-01-21 PHEAA-based high-toughness hydrogel and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110084508.4A CN112940180B (en) 2021-01-21 2021-01-21 PHEAA-based high-toughness hydrogel and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112940180A CN112940180A (en) 2021-06-11
CN112940180B true CN112940180B (en) 2023-05-02

Family

ID=76235764

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110084508.4A Active CN112940180B (en) 2021-01-21 2021-01-21 PHEAA-based high-toughness hydrogel and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112940180B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RO112883B1 (en) * 1996-05-15 1998-01-30 Maria Caloianu Bioartificial hydrogels with advanced hygroscopicity
WO2004031253A1 (en) * 2002-10-02 2004-04-15 Coloplast A/S A hydrogel
CN102226007B (en) * 2011-04-12 2012-09-05 厦门大学 Double network polymer hydrogel and preparation method thereof
CN109971105A (en) * 2019-03-15 2019-07-05 浙江工业大学 A kind of chitosan/poly- N- hydroxyethyl acrylamide is tough anti-pollution double-network hydrogel and preparation method thereof

Also Published As

Publication number Publication date
CN112940180A (en) 2021-06-11

Similar Documents

Publication Publication Date Title
Lin et al. A bioinspired hydrogen bond crosslink strategy toward toughening ultrastrong and multifunctional nanocomposite hydrogels
US11033658B2 (en) Interpenetrating networks with covalent and ionic crosslinks
Dragusin et al. Novel gelatin–PHEMA porous scaffolds for tissue engineering applications
Bartnikowski et al. Protective effects of reactive functional groups on chondrocytes in photocrosslinkable hydrogel systems
CN109651623B (en) Method for improving adhesion performance of polyacrylamide hydrogel and obtained polyacrylamide hydrogel
CN107033371B (en) A kind of preparation method of photo crosslinked polyethylene alcohol/nanocrystalline cellulose PVA/CNC composite hydrogel
CN114736397B (en) Preparation method and application of wet adhesive hydrogel for dura mater injury repair
CN109836596A (en) The high-intensitive preparation method with the amylopectin composite hydrogel of high adherency of strong hydrogen bonding effect
CN113788960A (en) Preparation method of polyvinyl alcohol-acrylamide-agarose hydrogel with high mechanical strength
CN113292671A (en) Polymer crosslinking agent containing phenylboronic acid group, biological adhesive prepared from polymer crosslinking agent, and preparation method and application of biological adhesive
CN112940180B (en) PHEAA-based high-toughness hydrogel and preparation method and application thereof
CN114699555B (en) Preparation method of anti-swelling wet-bonding artificial dura mater
CN108003357A (en) Catechu aldehyde crosslinked with collagen hydrogel and preparation method thereof
WO2023024055A1 (en) Preparation method of polyvinyl alcohol-acrylamide -agarose hydrogelwith high mechanical strength
CN112940294A (en) PVA/HA double-network hydrogel and preparation method and application thereof
CN112940173B (en) PHEMA-based high-toughness hydrogel and preparation method and application thereof
WO2019208576A1 (en) Hydrogel and method for producing hydrogel
CN109880011A (en) A kind of articular cartilage superficial layer repairs multiplexing high-efficiency selfreparing hydrogel and preparation method thereof
Idris et al. Influence of gamma irradiation on polymerization of pyrrole and glucose oxidase immobilization onto poly (pyrrole)/poly (vinyl alcohol) matrix
CN110755677B (en) Polyamino acid hydrogel dressing and preparation method and application thereof
CN113577370A (en) Janus hydrogel adhesive and preparation method and application thereof
CN113861447A (en) Modified hydroxypropyl chitosan adhesive self-healing hydrogel and preparation method and application thereof
Xiao et al. Strong and Tough Biofibers Designed by Dual Crosslinking for Sutures
CN113999630A (en) Adhesive and preparation method and application thereof
Fonseca et al. Facile Synthesis of Highly Stretchable, Tough, and Photodegradable Hydrogels

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