CN114209891A - Wet-state-adhered super-lubricating hydrogel coating and preparation method thereof - Google Patents
Wet-state-adhered super-lubricating hydrogel coating and preparation method thereof Download PDFInfo
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- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
- A61L29/145—Hydrogels or hydrocolloids
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- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
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- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
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- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/10—Materials for lubricating medical devices
Abstract
The invention provides a wet-state adhered super-lubricating hydrogel coating and a preparation method thereof. Adding hydrogel monomer and sodium alginate powder into deionized water, and sequentially adding cross-linking agentN,N'Methylene bisacrylamide, a crosslinking accelerator tetramethylethylenediamine, a hydrophilic photoinitiator ammonium persulfate and an ionic crosslinking agent calcium sulfate dihydrate are added, and then an adhesive is added and mixed uniformly to obtain a pre-gel solution; and immersing the substrate in the pre-gel solution, taking out, placing at room temperature for illumination, and carrying out photoinitiation to complete polymerization reaction to obtain the wet-state adhered super-lubricating hydrogel coating. The obtained hydrogel has a double-network water structure, can effectively dissipate applied stress, has good mechanical properties, and effectively solves the problems of fracture and deformation of the coating caused by bending; simultaneously has good hydrophilicity and good adhesion. The hydrogel coating is convenient to use, can form a film quickly, and is expected to be applied to medical catheters, Foley catheters and cardiac pacingWire guides and large-scale soft robots.
Description
The technical field is as follows:
the invention belongs to the field of medical instruments, and particularly relates to a wet-state adhered super-lubricating hydrogel coating and a preparation method thereof.
Background art:
water lubrication is extensiveAre present in many anatomical sites of the organism, including the respiratory tract, articular cartilage, internal organs, and ocular surfaces. Good lubrication and low friction movement play a vital role in maintaining the physiological function of the human body. Thus, low boundary friction against tissue is advantageous for medical device applications, but these medical devices generally lack the ability for biological interface lubrication. According to current research, the hydration layer formed on the underlying substrate is referred to as aqueous solution lubrication. The trapped water in the hydrated layer is an important lubricant between the sliding surfaces, and when subjected to shear forces, the hydrated layer can respond in a fluid-like manner to minimize drag, resulting in a small coefficient of friction (CoF) (Ying Han,et al. Self-adhesive lubricated coating for enhanced bacterial resistance. Bioact. Mater., 2021, 6, 2535−2545）。
existing methods of achieving an interfacial lubricious surface rely primarily on grafted hydrophilic polymer brushes or coated hydrogel layers. For example, using a reversible addition fragmentation chain transfer (RAFT) polymerization process, a number of diblock copolymers with different lubricating blocks were synthesized, with a large reduction in CoF observed; poly (2-methacryloylethylphosphorylcholine) brushes were covalently bonded to the pretreated mica surface by atom transfer methyl polymerization (ATRP). Due to the high hydration of the hydrophilic polymer brush, the CoF of the coating was reduced to 10−3. These methods have some limitations. Implanted polymer brushes are easily damaged and, due to their nanoscale thickness, do not provide sufficient mechanical compliance. Hydrogel coatings are only suitable for relatively simple geometries, precluding their use for surfaces having complex geometries and features.
Another common strategy is to coat the surface of the device with a hydrogel layer, since hydrogels have good mechanical and chemical similarity to biological tissues. Interfacial bonding between hydrogels and polymer substrates has been one of the most widely used strategies to incorporate soft hydrogel coatings on various polymer devices. In this method, the hydrogel coating is typically introduced into the polymeric device in the form of a solid preformed crosslinked network or a liquid pre-gel solution, which is then cured at the surface. For example, chinese patent publication No. CN201911214849.8 discloses a hydrophilic lubricating coating, which has better mechanical robustness, but insufficient adhesion, and is liable to cause peeling of the coating. Further, as disclosed in chinese patent publication No. CN202110691314.0, a hydrogel lyophilized powder coating is disclosed, which solves the problem of dehydration and peeling of hydrogel due to long-term storage, but has a problem of uneven coating, and a hydrogel coating made by molding or dip coating generally generates a relatively thick hydrogel layer (over 50 μm) whose shape is determined by the shape of the surface of the mold or dip coating used. These problems greatly hinder the ability of the coating to accommodate complex surface geometries and fine-feature devices.
The double-network structure provided by the research has good mechanical properties, and in addition, the hydrogel has strong hydrophilic groups such as amino groups and carboxyl groups, and the like, and forms strong hydrogen bonds with water to fix water molecules on the surface of the gel, so that the lubricating effect is achieved. The addition of the adhesive rich in hydrophilic groups such as phenolic hydroxyl groups (such as chitosan, tannic acid and dopamine), carboxyl groups (such as sodium alginate) and the like endows the hydrogel with a strong adhesion function, and is beneficial to the coating to adapt to catheters with various irregular shapes. The prepared hydrogel coating shows the flexibility of a tissue sample (Young modulus is approximately equal to 30 kPa), has uniform and adjustable thickness within the range of 5-50 mu m, can bear long-time shearing force, and has no measurable damage. Hydrogel skins also provide a superior low friction, stain resistant, and ion conductive surface without affecting their original mechanical properties and geometry. Improved application of hydrogel coatings to the interior and exterior surfaces of various practical polymer devices, including medical catheters, Foley catheters, cardiac pacemaker leads, and large-scale soft robots.
The invention content is as follows:
the invention aims to provide a wet-state adhered super-lubricating hydrogel coating and a preparation method thereof, and the prepared hydrogel has good adhesiveness, mechanical property and self-repairability. More significantly, the hydrogel also has a super-lubricious effect after being wetted with water. The coating can be coated on the surface of an irregular catheter to form a uniform coating so as to relieve the discomfort of a patient in the intubation process and the inflammation problem caused by the discomfort, and is expected to be applied to the fields of medical catheters, Foley catheters, cardiac pacemaker leads, large-scale soft robots and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a wet-adherent super-lubricating hydrogel coating, comprising the steps of:
(1) adding a hydrogel monomer and sodium alginate powder into deionized water, and uniformly stirring the solution to completely mix the hydrogel monomer and the sodium alginate powder to obtain a solution A;
(2) adding the cross-linking agent into the solution A in sequenceN,N'Sufficiently stirring and uniformly mixing Methylene Bisacrylamide (MBAA), cross-linking accelerator Tetramethylethylenediamine (TEMED), hydrophilic photoinitiator Ammonium Persulfate (APS) and ionic cross-linking agent calcium sulfate dihydrate to obtain a solution B;
(3) adding the adhesive into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C;
(4) and (3) immersing the catheter in the pre-gel solution C for 2s, taking out, placing at room temperature for illumination, and carrying out photoinitiation to complete polymerization reaction to obtain the wet-state adhered super-lubricating hydrogel coating.
In the above method, the hydrogel monomer in the step (1) is acrylamide, acrylic acid,N,N-one or more of dimethylacrylamide, methacrylic acid and hydroxyethyl methacrylate.
In the method, the concentration of the hydrogel monomer in the step (1) is 5-30%W/VThe concentration of sodium alginate is 2-10%W/VThe stirring time is 6-24 h.
In the above process, the crosslinking agent described in the step (2)N,N'The concentration of the-methylene bisacrylamide is 0.01-0.1%W/VThe concentration of the cross-linking accelerator tetramethylethylenediamine is 0.05-0.50%W/VThe concentration of the hydrophilic photoinitiator ammonium persulfate is 0.1-0.15%W/VThe concentration of the ionic crosslinking agent calcium sulfate dihydrate is 0.1-0.4%W/VThe stirring time is 6-24 h.
In the method, the adhesive in the step (3) is a substance rich in hydrophilic groups such as phenolic hydroxyl groups and carboxyl groups; (ii) a Including but not limited to: chitosan, tannic acid, dopamine and sodium alginate.
In the above method, the mass ratio of the binder to the hydrogel monomer contained in the solution B is 0.01 to 0.5: 100.
in the method, the illumination in the step (4) is ultraviolet illumination or visible illumination, and the illumination time is 0.5-4 h.
In the method, the time of the hydrogel polymerization reaction in the step (4) is 12-24 h.
A wet-adherent super-lubricating hydrogel coating prepared by the method.
The wet-state adhered super-lubricating hydrogel coating is applied to the field of medical appliances.
Compared with the prior art, the invention has the following advantages:
(1) the hydrogel prepared by the invention has double networks, has high mechanical strength, can dissipate stress applied from the outside as a medical catheter coating, and is not easy to damage and deform.
(2) The invention adds the adhesive, provides strong adhesion, can form a coating on an irregular surface, and can adjust the thickness of the coating by adjusting the proportion of the adhesive.
(3) The hydrogel is a hydrophilic material, has a small friction coefficient, and can relieve the pain of a patient when being used as a medical catheter coating.
Description of the drawings:
FIG. 1 is a measurement of hydrophilicity of the double-network composite hydrogel prepared in example 7.
FIG. 2 is a mechanical property analysis of the double-network composite hydrogel prepared in example 7.
FIG. 3 is a graph showing the verification of the adhesive properties of the double-network composite hydrogel prepared in example 7. A, an adhesion physical graph of hydrogel to different substrates; b: adhesion strength of hydrogels to different substrates.
FIG. 4 is a diagram of the adhesion mechanism of a double-network composite hydrogel.
Fig. 5 is a self-healing performance verification and mechanism diagram of the double-network composite hydrogel prepared in example 7. A: self-healing hydrogel object images; b: a self-healing mechanism diagram of the hydrogel.
The specific implementation scheme is as follows:
for a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The invention discloses a wet-state adhered super-lubricating hydrogel coating, which is prepared by the following steps:
firstly, adding a hydrogel monomer and sodium alginate powder into deionized water, and uniformly stirring the solution to completely mix the hydrogel monomer and the sodium alginate powder to obtain a solution A;
adding the cross-linking agents in sequenceN,N'Putting Methylene Bisacrylamide (MBAA), cross-linking accelerator Tetramethylethylenediamine (TEMED), hydrophilic photoinitiator ammonium persulfate and ionic cross-linking agent calcium sulfate dihydrate into the solution A, and fully stirring and uniformly mixing to obtain a solution B;
adding the adhesive into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C;
and (3) immersing the conduit in the pre-gel solution C, taking out after 2s, placing at room temperature for illumination, and completing polymerization reaction through photoinitiation to obtain the wet-state adhered super-lubricating hydrogel.
In the invention, firstly, a hydrogel monomer and sodium alginate powder are dissolved in deionized water to obtain a high-molecular solution A, wherein the concentration of the hydrogel monomer is 5-30%W/VThe concentration of sodium alginate is 2-10%W/VThe stirring time is 6-24 h. More preferably, the concentration of hydrogel monomer is 12-18%W/VThe concentration of the sodium alginate is 4-6%W/VThe stirring time is 15-24 h.
Then, the crosslinking agent is added in sequenceN,N'Methylene Bisacrylamide (MBAA), cross-linking accelerator Tetramethylethylenediamine (TEMED), hydrophilic photoinitiator ammonium persulfate and ionic cross-linking agent calcium sulfate dihydrate are stirred and mixed uniformly to obtain solution B; the crosslinking agentN,N'The concentration of the-methylene bisacrylamide is 0.01-0.1%W/VCrosslinking ofThe concentration of promoter tetramethylethylenediamine is 0.05-0.50%W/VThe concentration of the hydrophilic photoinitiator ammonium persulfate is 0.1-0.15%W/VThe concentration of the ionic crosslinking agent calcium sulfate dihydrate is 0.1-0.4%W/VThe stirring time is 6-24 h. More preferably, the crosslinking agentN,N'The concentration of the-methylene bisacrylamide is 0.04-0.08%W/VThe concentration of the crosslinking accelerator tetramethylethylenediamine is 0.2-0.38%W/VThe concentration of the hydrophilic photoinitiator ammonium persulfate is 0.12-0.14%W/VThe concentration of the ionic crosslinking agent calcium sulfate dihydrate is 0.2-0.3%W/VStirring for 12-17 h;
the mass ratio of the added adhesive to the hydrogel monomer is 0.01-0.5: 100. more preferably, the mass ratio of the adhesive to the hydrogel monomer is 0.05 to 0.2: 100. the adhesive is a substance rich in hydrophilic groups such as phenolic hydroxyl and carboxyl; including but not limited to chitosan, tannic acid, dopamine, sodium alginate.
The illumination is ultraviolet or visible illumination, and the illumination time is 0.5-4 h. More preferably, the illumination time is 1-2 h.
For further understanding of the present invention, the multifunctional light-driven low temperature resistant double-network hydrogel and the preparation method thereof provided by the present invention are illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
First 5%, (W/V）2%, (ii) an acrylamide monomerW/V）Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.01%, (W/V）Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.05%, (W/V）0.1 percent of (2)W/V）0.2% (ii) of ammonium persulfate andW/V）stirring the ionic crosslinking agent calcium sulfate dihydrate for 6 hours, and uniformly mixing to obtain a solution B;
adding adhesive tannic acid into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added tannic acid to the hydrogel monomer contained in the solution B is 0.01: 100, respectively;
and immersing the catheter in the pre-gel solution C for 2s, taking out, standing at room temperature for 12 h after placing under ultraviolet light for 0.5 h to finish polymerization, and obtaining the chemically crosslinked strong-adhesion double-network composite hydrogel coating through photo-initiation.
Example 2
First, 15%, (W/V) 2%, (ii) an acrylamide monomerW/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.32%, (W/V) 0.13% ((ii) tetramethylethylenediamine) as a crosslinking acceleratorW/V) 0.25% (ii) of ammonium persulfate andW/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 6 hours, and uniformly mixing to obtain a solution B;
adding adhesive chitosan into the solution B, and fully stirring until the chitosan and the solution B are uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added chitosan to the hydrogel monomer contained in the solution B is 0.01: 100, respectively;
and immersing the catheter in the pre-gel solution C for 2s, taking out, standing at room temperature for 12 h after placing under ultraviolet light for 0.5 h to finish polymerization, and obtaining the chemically crosslinked strong-adhesion double-network composite hydrogel coating through photo-initiation.
Example 3
First 30%, (W/V) Acrylic acid monomer, 5%, (W/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.1%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.50%, (W/V) 0.15 percent of (2)W/V) 0.3% (ii) of ammonium persulfate andW/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 24 hours, and uniformly mixing to obtain a solution B;
adding dopamine serving as an adhesive into the solution B, and fully stirring until the dopamine is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added dopamine to the hydrogel monomer contained in the solution B is 0.01: 100, respectively;
and immersing the conduit in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for illumination for 0.5 h, standing for 12 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion double-network composite hydrogel coating.
Example 4
First 5%, (W/V) Is/are as followsN,N-dimethylacrylamide monomer, 10% (ii) acrylamide monomerW/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.05%, (W/V) 0.1 percent of (2)W/V) 0.2% (ii) of ammonium persulfate andW/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 24 hours, and uniformly mixing to obtain a solution B;
adding adhesive tannic acid into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added tannic acid to the hydrogel monomer contained in the solution B is 0.05: 100, respectively;
and immersing the conduit in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for illumination for 0.5 h, standing for 12 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion double-network composite hydrogel coating.
Example 5
First, 15%, (W/V) 2%, (ii) of a methacrylic acid monomerW/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.32%, (W/V) 0.13% ((ii) tetramethylethylenediamine) as a crosslinking acceleratorW/V) 0.25% (ii) of ammonium persulfate andW/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 12 hours, and uniformly mixing to obtain a solution B;
adding adhesive chitosan into the solution B, and fully stirring until the chitosan and the solution B are uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added chitosan to the hydrogel monomer contained in the solution B is 0.05: 100, respectively;
and immersing the conduit in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for illumination for 0.5 h, standing for 18 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion double-network composite hydrogel coating.
Example 6
First, 15%, (W/V) 5% (ii) hydroxyethyl methacrylate monomerW/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.32%, (W/V) Tetramethylethylenediamine, (0.13%, (W/V) Ammonium persulfate and (0.25%, (W/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 12 hours, and uniformly mixing to obtain a solution B;
adding dopamine serving as an adhesive into the solution B, and fully stirring until the dopamine is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added dopamine to the hydrogel monomer contained in the solution B is 0.05: 100, respectively;
and immersing the conduit in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for illumination for 1.5 h, standing for 12 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion double-network composite hydrogel coating.
Example 7
First, 15%, (W/V) Acrylamide monomer, 5%, (W/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.32%, (W/V) Tetramethylethylenediamine, (0.13%, (W/V) Ammonium persulfate and (0.25%, (W/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 12 hours, and uniformly mixing to obtain a solution B;
adding adhesive tannic acid into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added tannic acid to the hydrogel monomer contained in the solution B is 0.05: 100, respectively;
immersing the catheter in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for illumination for 1.5 h, standing for 18 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion polyacrylamide/sodium alginate/tannic acid (PAAM/SA/TA) double-network composite hydrogel coating.
FIG. 1 is a graph showing the hydrophilicity of PAAM/SA/TA double-network composite hydrogel of example 7, which is measured by the contact angle of 30.7 degrees. + -. 1.1 degrees, showing good hydrophilicity, thereby providing a lubricating effect to the coating.
Fig. 2 is a qualitative and quantitative analysis chart of the mechanical properties of the PAAM/SA/TA double-network composite hydrogel of example 7, which respectively tests the tensile strength and the young's modulus of the above materials, and clearly shows that the compressive strength and the young's modulus of the hydrogel in a compressed state are respectively: 145.3 kPa, 181.6 kPa; the tensile strength and Young modulus of the hydrogel in a tensile state are respectively as follows: 101.1 kPa, 10.06 kPa.
FIG. 3 is a verification of the adhesion performance of PAAM/SA/TA double-network composite hydrogel prepared in example 7, which can be adhered to the surface of a (PET, glass, skin, PP, metal, paper) substrate and has the adhesion strength of up to 60.79 kPa. The adhesion mechanism mainly depends on abundant phenolic hydroxyl, carboxyl and amino groups on the adhesive, and the mechanism is shown in figure 4.
FIG. 5 is a graph showing the self-healing performance of PAAM/SA/TA double-network composite hydrogel prepared in example 7, which is verified by Ca2+And reversible ionic bonds formed between the hydrogel and carboxylate ions enable the hydrogel to have good self-healing performance, and the self-healing can be completed after the hydrogel is fractured for 12 hours.
Example 8
First, 15%, (W/V) Acrylamide monomer, 5%, (W/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.32%, (W/V) Tetramethylethylenediamine, (0.13%, (W/V) Ammonium persulfate and (0.25%, (W/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 12 hours, and uniformly mixing to obtain a solution B;
adding adhesive tannic acid into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added tannic acid to the hydrogel monomer contained in the solution B is 0.20: 100, respectively;
and immersing the conduit in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for illumination for 1.5 h, standing for 18 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion double-network composite hydrogel coating.
Example 9
First, 15%, (W/V) Is/are as followsN,N-dimethylacrylamide monomer, 5%, (W/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.32%, (W/V) 0.13% ((ii) tetramethylethylenediamine) as a crosslinking acceleratorW/V) 0.25% (ii) of ammonium persulfate andW/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 12 hours, and uniformly mixing to obtain a solution B;
adding adhesive tannic acid into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added tannic acid to the hydrogel monomer contained in the solution B is 0.05: 100, respectively;
and immersing the conduit in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for 2 h, standing for 18 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion double-network composite hydrogel coating.
Example 10
First, 15%, (W/V) Acrylic acid monomer, 5%, (W/V) Dissolving sodium alginate powder in deionized water, and stirring the solution for 18 h to mixCompletely mixing to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.32%, (W/V) 0.13% ((ii) tetramethylethylenediamine) as a crosslinking acceleratorW/V) 0.25% (ii) of ammonium persulfate andW/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 12 hours, and uniformly mixing to obtain a solution B;
adding adhesive tannic acid into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added tannic acid to the hydrogel monomer contained in the solution B is 0.5: 100, respectively;
and immersing the conduit in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for 2 h, standing for 24 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion double-network composite hydrogel coating.
Comparative example 1
First, 15%, (W/V) Acrylamide monomer, 5%, (W/V) Dissolving the sodium alginate powder in deionized water, and uniformly stirring the solution for 18 hours to completely mix the solution to obtain a solution A;
adding 0.05%, (W/V) Cross-linking agent of (2)N,N'Methylene bisacrylamide, 0.32%, (W/V) 0.13% ((ii) tetramethylethylenediamine) as a crosslinking acceleratorW/V) 0.25% (ii) of ammonium persulfate andW/V) Stirring the ionic crosslinking agent calcium sulfate dihydrate for 12 hours, and uniformly mixing to obtain a solution B;
adding adhesive tannic acid into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C; the mass ratio of the added tannic acid to the hydrogel monomer contained in the solution B is 1: 100, respectively;
and immersing the conduit in the pre-gel solution C for 2s, taking out, placing under ultraviolet light for illumination for 1.5 h, standing for 18 h to complete polymerization, and carrying out photo-initiation to obtain the chemically crosslinked strong-adhesion double-network composite hydrogel coating.
The super-lubricating coatings provided in examples 1-10 and comparative example 1 were tested for adhesion, lubricity, hydrophilicity, coating thickness, and mechanical properties as follows:
(1) adhesion test
The specific method comprises the following steps: the hydrogel adhesion performance was tested using an instrument 1185 (instrument, boston, MA, USA) according to lap shear test standard (astm f 2255-05). Cutting fresh Corii Sus Domestica into 4.0 cm × 1.0 cm rectangular slices, directly coating hydrogel on two opposite sides of two substrates with contact area of 1.0 × 1.0 cm2. After the substrate was contacted for 40 min at a pressure of 250.0 g, it was placed into a testing machine to evaluate the adhesive strength of the hydrogel at room temperature.
(2) Self healing experiment
The specific method comprises the following steps: to evaluate the self-healing ability of the hydrogel in water, pieces of hydrogel (30.0 mm. times.5.0 mm. times.2.0 mm) were cut into two pieces with a surgical blade, and the experiment was conducted in three groups. The two separated fragments were then brought into contact with each other with a small amount of external force and left at 25 ℃ for 1 min. Also, the two separated parts were brought into contact with each other in the air under a slight external force and left at room temperature (25 ℃) for 12 h, 24 h, 36 h. The mechanical properties of the healed hydrogel were tested according to "mechanical experiments". Each group was subjected to 3 replicates.
(3) Contact Angle test
The specific method comprises the following steps: the surface contact angle of the hydrogel in contact with deionized water was measured using a drop shape analysis system DSA100 (Kruss, Hamburg, germany). In the first 5 min of the experiment, the hydrogel was cut into 2.0X 0.2 cm pieces3Size section. A drop of water (5.0 μ L) was deposited on the sample surface using DSA1.8 software, and the contact angle value was measured.
(4) Mechanics experiment
The measurement of tensile strength was used by texture analyzer (SMS ltd) to measure the mechanical properties of the composite hydrogel. Each sample was cut into a rectangular sheet having dimensions of 30.0 mm. times.5.0 mm. times.2.0 mm, and a tensile test was conducted until breakage at a tensile rate of 10.0 mm/min.
(5) Friction test
Surface lubrication characteristics were measured by a pin-on-disk tribometer (UMT-triboLab, Bruker, USA). Hardened steel balls (diameter =6 mm) were rubbed on a previously prepared substrate (size =1.5 cm × 2 cm). The coefficient of friction (CoF) was measured by linear reciprocation in deionized water at room temperature. The applied load and the sliding speed were set to 5N and 5 mm/s, respectively.
It is to be noted that the samples in the examples of the present invention were lubricating hydrogels prepared under the same conditions and tested for adhesion, hydrophilicity, mechanical and frictional properties.
The results of the above tests are shown in table 1 below:
TABLE 1 comparison of basic Properties of hydrogel coatings of different Components
As can be seen from table 1, in comparative example 1, the adhesion was enhanced and the contact angle and the frictional force were not greatly changed by increasing the amount of the binder compared to examples 1 to 10. In contrast, the same hydrogel samples had increased binder loading and reduced mechanical strength compared to example 7. Not enough to withstand the forces generated during bending of the catheter.
The above embodiments are merely provided to aid understanding of the method of the present invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of a wet-state adhered super-lubricating hydrogel coating is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a hydrogel monomer and sodium alginate powder into deionized water, and uniformly stirring the solution to completely mix the hydrogel monomer and the sodium alginate powder to obtain a solution A;
(2) adding the cross-linking agent into the solution A in sequenceN,N'Sufficiently stirring and uniformly mixing methylene bisacrylamide, a crosslinking accelerator tetramethyl ethylenediamine, a hydrophilic photoinitiator ammonium persulfate and an ionic crosslinking agent calcium sulfate dihydrate to obtain a solution B;
(3) adding the adhesive into the solution B, and fully stirring until the mixture is uniformly mixed to obtain a pre-gel solution C;
(4) and immersing the conduit in the pre-gel solution C for 2s, taking out, placing at room temperature for illumination, and carrying out photoinitiation to complete polymerization reaction to obtain the wet-state adhered super-lubricating hydrogel coating.
2. The method of claim 1, wherein: the hydrogel monomer in the step (1) is acrylamide, acrylic acid,N,N-one or more of dimethylacrylamide, methacrylic acid and hydroxyethyl methacrylate.
3. The method of claim 1, wherein: the concentration of the hydrogel monomer in the step (1) is 5-30% W/V, the concentration of sodium alginate is 2-10% W/V, and the stirring time is 6-24 h.
4. The method of claim 1, wherein: the crosslinking agent in the step (2)N,N'The concentration of the-methylene bisacrylamide is 0.01-0.1% W/VThe concentration of the crosslinking accelerator tetramethylethylenediamine was 0.05−0.50% W/VThe concentration of the hydrophilic photoinitiator ammonium persulfate is 0.1-0.15%W/VThe concentration of the ionic crosslinking agent calcium sulfate dihydrate is 0.1-0.4%W/VThe stirring time is 6-24 h.
5. The method of claim 1, wherein: the adhesive in the step (3) is a substance rich in phenolic hydroxyl groups or hydrophilic groups rich in carboxyl groups; including but not limited to: chitosan, tannic acid, dopamine and sodium alginate.
6. The method of claim 1, wherein: the mass ratio of the adhesive to the hydrogel monomer contained in the solution B in the step (3) is 0.01-0.5: 100.
7. the method of claim 1, wherein: the illumination in the step (4) is ultraviolet illumination or visible illumination, and the illumination time is 0.5-4 h; the time of the polymerization reaction is 12-24 h.
8. A wet-adherent super-lubricious hydrogel prepared by the method of claim 1.
9. Use of the wet-adherent super-lubricious hydrogel of claim 9 in the field of medical devices.
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