CN114456309B - Reusable zwitterion medical adhesive and preparation method thereof - Google Patents

Reusable zwitterion medical adhesive and preparation method thereof Download PDF

Info

Publication number
CN114456309B
CN114456309B CN202210298700.8A CN202210298700A CN114456309B CN 114456309 B CN114456309 B CN 114456309B CN 202210298700 A CN202210298700 A CN 202210298700A CN 114456309 B CN114456309 B CN 114456309B
Authority
CN
China
Prior art keywords
percent
zwitterionic
reusable
medical adhesive
initiator
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
CN202210298700.8A
Other languages
Chinese (zh)
Other versions
CN114456309A (en
Inventor
李利
王瑜明
沈健
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.)
Nanjing Normal University
Original Assignee
Nanjing 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 Nanjing Normal University filed Critical Nanjing Normal University
Priority to CN202210298700.8A priority Critical patent/CN114456309B/en
Publication of CN114456309A publication Critical patent/CN114456309A/en
Application granted granted Critical
Publication of CN114456309B publication Critical patent/CN114456309B/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
    • C08F220/10Esters
    • C08F220/38Esters containing sulfur
    • C08F220/387Esters containing sulfur and containing nitrogen and oxygen
    • 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08F4/00Polymerisation catalysts
    • C08F4/40Redox systems

Abstract

The invention discloses a reusable zwitterion medical adhesive and a preparation method thereof; uniformly mixing a zwitterionic monomer, an initiator, a cross-linking agent, deionized water and other functional monomers in an ice-water bath according to the content range of the components; transferring the uniformly mixed reaction solution into a mold by using a glass mold as a preparation template, and carrying out free radical polymerization to obtain a zwitterion adhesive; the adhesive prepared by the invention has good adhesion performance, strong absorption capacity to body fluid, simple and convenient preparation, and good biocompatibility and reusability.

Description

Reusable zwitterion medical adhesive and preparation method thereof
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a reusable zwitterion medical adhesive and a preparation method thereof.
Background
Although sutures are considered the mainstay of several treatments and procedures in general surgery, they also have some drawbacks, mainly associated with high infection rates, extensive handling, risk of blood-borne diseases and tissue reactivity. For these reasons, the trend toward simpler, faster minimally invasive surgical procedures has encouraged the development of sutureless techniques, such as the use of adhesive bonding to restore soft tissue integrity and functionality. The use of medical adhesives by humans has a long history, and early medical adhesives were mainly prepared by simply mixing some natural high molecular substances. In recent decades, research on medical adhesive materials has been rapidly developed driven by the great clinical demand. At present, the medical adhesives commonly used are mainly classified into three types, which are natural adhesives, semisynthetic adhesives, and synthetic adhesives. However, the existing medical adhesives have certain defects, such as easy bacterial infection of fibrin glue and certain toxicity of cyanoacrylate adhesives.
The positive and negative charges of the molecules of the zwitterionic structure produce a high dipole moment. This strong dipole property enables the zwitterionic hydrogels to establish good adhesion on many surfaces through ion-dipole or dipole-dipole interactions and the ion dipole and dipole-dipole interactions of the adherend repeatedly adhere to a variety of substrates. The zwitterionic polymer has hydrophilic anionic and cationic groups, can be highly hydrated and has unique anti-biological pollution performance, namely, the amphoteric zwitterionic polymer can resist the adsorption of nonspecific proteins, bacterial adhesion and the formation of biological membranes, and the characteristic enables the materials to be increasingly applied to the relevant fields of biomedicine and the like. Based on anti-biofouling properties, zwitterionic polymers can be used in antifouling coatings, antimicrobial coatings, biomedical diagnostics, drug delivery, gene delivery vehicles, separation membranes, and ship coatings. Based on excellent biocompatibility of zwitterion, the adhesive which is easy to synthesize, good in biocompatibility and reusable can be prepared only by applying the zwitterion to the adhesive through simple modification.
Disclosure of Invention
In order to solve the problems, the invention discloses a reusable zwitterion medical adhesive and a preparation method thereof, and solves the problems that the existing adhesive is high in cytotoxicity, poor in antibacterial performance, incapable of being reused and the like. The invention takes zwitterionic monomer as main raw material, and prepares an adhesive with good biocompatibility by matching two functional monomers through physical crosslinking.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention aims to provide a reusable zwitterionic medical adhesive which consists of the following components in percentage by mass:
30-40% of zwitterionic monomer;
1.5 to 5 percent of functional monomer;
2.5 to 5 percent of functional monomer;
0.5 to 2 percent of initiator;
0.5 to 2 percent of cross-linking agent;
the balance of deionized water.
Further, the zwitterionic monomer is a compound with a positively and negatively charged dipole ion and is electrically neutral.
Further, the zwitterionic monomer is methacrylethyl sulfobetaine.
Further, the functional monomer 1 is one of hydroxyethyl methacrylate, hydroxyethyl acrylate and N-isopropylacrylamide.
Further, the functional monomer 2 is one of triethylene glycol dimethacrylate, 1-vinylimidazole or ethylene glycol dimethacrylate.
Further, the initiator is a redox initiator.
Further, the oxidant in the initiator is one of potassium persulfate, ammonium persulfate and cumene hydroperoxide; the reducing agent in the initiator is one of sodium bisulfite, tetramethyl ethylenediamine and ferrous chloride.
Further, the cross-linking agent is hectorite.
It is yet another object of the present invention to provide a method for preparing a reusable zwitterionic medical adhesive, comprising the steps of:
s01, dispersing the cross-linking agent in deionized water at constant temperature until the cross-linking agent is completely dissolved;
s02, sequentially adding a zwitterion monomer into the solution obtained in the step S01, and obtaining a mixed solution by using a functional monomer 1 and a functional monomer 2;
s03, adding an oxidant in an initiator into the mixed solution obtained in the step S02, and adding a reducing agent after 5-10 minutes;
and S04, transferring the solution obtained in the step S03 to a glass mold for reaction to obtain a finished adhesive product.
Further, the constant temperature in the step S01 is 0-20 ℃, the reaction temperature in the step S04 is 10-25 ℃, and the reaction time is 18-36 hours.
After the synthesis of the adhesive of the present invention was completed, the adhesive was coated on the treated fresh pigskin, and the peel strength, i.e., the adhesive strength of the adhesive, was tested by a lap shear test. A hydrogel sample with the length of 10mm and the thickness of 2mm is adhered between two pieces of pigskin (the length of the pigskin is 50mm, and the width of the pigskin is 10 mm), and the hydrogel sample is pressed for 30s to be fully contacted with the surface of the pigskin. The peel strength was measured by an electronic universal tester (WDW-5). The lower end pigskin is clamped in a clamp fixed at the bottom, the upper end pigskin is clamped in a clamp pulled upwards, and the speed of upward pulling in the test process is 20mm/min. After which it is pressed again for bonding, giving the adhesive repeated bonding properties after a number of tests.
The invention has the beneficial effects that:
compared with the existing medical adhesive, the medical adhesive has the advantages that the good biocompatibility is endowed to the adhesive through the zwitterion modification, the infection risk of wounds is reduced, and due to the excellent hydrophilic performance and the special structure of the zwitterion and the introduced functional monomer 1 and functional monomer 2, the body fluid absorption capacity of the adhesive is improved, the adhesive can be repeatedly adhered, and the wound healing is promoted.
Drawings
FIG. 1 is a graph showing the results of measuring the peel strength of adhesives obtained in examples 1 to 5 of the present invention and comparative example 1;
FIG. 2 is a graph showing the results of measuring the peel strength of adhesives obtained in examples 6 to 10 according to the present invention and comparative example 2;
FIG. 3 is a graph showing the results of measuring the body fluid absorption capacity of the adhesive prepared in example 4 of the present invention;
FIG. 4 is a graph showing the results of measuring the repeated adhesion ability of the adhesive prepared in example 2 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, can be readily prepared from commercial sources or by methods known in the art.
Example 1
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 30%;
5% of N-isopropylacrylamide;
5% of 1-vinyl imidazole;
0.5 percent of potassium persulfate;
0.5 percent of tetramethyl ethylene diamine;
1.5 percent of hectorite;
and 57.5% of deionized water.
Adding 3ml of deionized water into a beaker, adding 1.5 percent of hectorite, magnetically stirring the mixture at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 30 percent of methacryloyl ethyl sulfobetaine, 5 percent of N-isopropyl acrylamide and 5 percent of 1-vinyl imidazole into the solution, then adding 0.5 percent of potassium persulfate serving as an oxidant in an initiator, adding 0.5 percent of tetramethylethylenediamine serving as a reducing agent after 5 to 10 minutes, and transferring the mixture into a glass mold after the complete dissolution to polymerize the mixture for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
Example 2
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 35%;
3% of N-isopropylacrylamide;
1% of 1-vinyl imidazole;
1% of potassium persulfate;
1% of tetramethyl ethylenediamine;
2% of hectorite;
and 57% of deionized water.
Adding 3ml of deionized water into a beaker, adding 2 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 35 percent of methacryloyl ethyl sulfobetaine, 3 percent of N-isopropyl acrylamide and 1-vinyl imidazole into the solution, then adding 1 percent of potassium persulfate serving as an oxidant in an initiator, adding 1 percent of tetramethyl ethylenediamine serving as a reducing agent after 5 to 10 minutes, and transferring the mixture into a glass mold after the complete dissolution to polymerize for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
Example 3
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 35%;
2% of N-isopropylacrylamide;
2% of 1-vinyl imidazole;
0.5 percent of potassium persulfate;
0.5 percent of tetramethyl ethylene diamine;
2% of hectorite;
and 58% of deionized water.
Adding 3ml of deionized water into a beaker, adding 2 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 35 percent of methacryloyl ethyl sulfobetaine, 2 percent of N-isopropyl acrylamide and 2 percent of 1-vinyl imidazole into the solution, then adding 0.5 percent of potassium persulfate serving as an oxidant in an initiator, adding 0.5 percent of tetramethyl ethylenediamine serving as a reducing agent after 5 to 10 minutes, and transferring the mixture into a glass mold after the complete dissolution to polymerize for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
Example 4
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 35%;
1% of N-isopropylacrylamide;
3% of 1-vinyl imidazole;
0.5 percent of potassium persulfate;
0.5 percent of tetramethyl ethylene diamine;
1.5 percent of hectorite;
and 58.5 percent of deionized water.
Adding 3ml of deionized water into a beaker, adding 1.5 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 35 percent of methacryloyl ethyl sulfobetaine, 1 percent of N-isopropyl acrylamide and 3 percent of 1-vinyl imidazole into the solution, then adding 0.5 percent of potassium persulfate serving as an oxidant in an initiator, adding 0.5 percent of tetramethylethylenediamine serving as a reducing agent after 5 to 10 minutes, and transferring the mixture into a glass mold after the complete dissolution to polymerize for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
Example 5
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
(ii) methacryloylethyl sulfobetaine 40%;
0.5 percent of N-isopropylacrylamide;
5% of 1-vinyl imidazole;
0.5 percent of potassium persulfate;
0.5 percent of tetramethyl ethylenediamine;
1.5 percent of hectorite;
and 52% of deionized water.
Adding 3ml of deionized water into a beaker, adding 1.5 percent of hectorite, magnetically stirring the mixture at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 40 percent of methacryloyl ethyl sulfobetaine, 0.5 percent of N-isopropyl acrylamide and 5 percent of 1-vinyl imidazole into the solution, then adding 0.5 percent of potassium persulfate serving as an oxidant in an initiator, adding 0.5 percent of tetramethylethylenediamine serving as a reducing agent after 5 to 10 minutes, transferring the mixture into a glass mold after the mixture is completely dissolved, and polymerizing the mixture for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
The zwitterionic medical adhesives prepared in examples 1-5 were characterized for peel strength, repeated peel, cytotoxicity, and body fluid absorption, and are shown in Table 1 and FIG. 1. The repeated peel of the adhesive prepared in example 2 and the body fluid absorption capacity of the adhesive prepared in example 4 are shown in fig. 4 and 3.
Method for characterizing peel strength: the adhesive was coated on the treated fresh pigskin and tested for peel strength, i.e., adhesive strength, by lap shear testing. A hydrogel sample having a length of 10mm and a thickness of 2mm was adhered between two pieces of pigskin (the length of the pigskin was 50mm, and the width was 10 mm), and the hydrogel sample was pressed for 30 seconds to be in full contact with the surface of the pigskin. The peel strength was measured by an electronic universal tester (WDW-5). The lower end pigskin is clamped in the clamp fixed at the bottom, the upper end pigskin is clamped in the clamp pulled upwards, and the upward pulling speed in the test process is 20mm/min. After which it is pressed again for bonding, giving the adhesive repeated bonding properties after a number of tests.
Characterization method for repeated peeling: the adhesive after the primary peeling test was re-adhered between two sheets of pigskin (pigskin length 50mm, width 10 mm), pressed with a 500g weight for 1 hour, and its peel strength was measured with an electronic universal tester (WDW-5). The lower end pigskin is clamped in a clamp fixed at the bottom, the upper end pigskin is clamped in a clamp pulled upwards, and the speed of upward pulling in the test process is 10 mm/min. The obtained result is recorded as effective data within 15% of the original peel strength.
Characterization method for cytotoxicity: adding L929 (mouse fibroblast) cells into a culture dish containing a DMEM culture medium as special cells for experiments, testing cytotoxicity of an adhesive by a live-dead cell staining method, putting the cells into each hole of a hole plate containing the materials, culturing the cells in a cell culture box at 37 ℃ for 24 hours, removing the DMEM culture medium, adding calcein (AM) and Propidium Iodide (PI) to stain the live-dead cells, and culturing the cells under the same conditions in the dark for 30 minutes. After the culture, the cells were observed for viability and death by an inverted fluorescence microscope.
Characterization method of body fluid absorption: the gelled adhesive groups were weighed and the mass recorded as M a . Placing the gel in a centrifuge tube filled with PBS buffer solution, respectively, taking out the adhesive within the time of 4 h,8 h,12 h,16 h,24 h (1 d), 2 d,3 d and 7 d, respectivelyRemoving water from the surface, weighing, after the adhesive has been equilibrated by imbibition, recording the mass as M b . The calculation formula for evaluating the absorption capacity of the adhesive for body fluid is as follows:
FA=(M b -M a )/ M a ×100%
table 1 shows the properties of the zwitterionic medical adhesives prepared in examples 1-5
Figure DEST_PATH_IMAGE002
As can be seen from Table 1, by varying the concentration of the various components in the hydrogel, the various properties of the zwitterionic medical adhesive can be effectively varied. The zwitterionic medical adhesive prepared under the experimental conditions of the invention has the advantages of high adhesive strength, good repeated stripping performance, good absorption capacity to body fluid and no cytotoxicity, and can meet the requirements of practical application.
Example 6
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 30%;
5% of hydroxyethyl acrylate;
ethylene glycol dimethacrylate 0.5%;
1% of ammonium persulfate;
1% of sodium bisulfite;
1.5 percent of hectorite;
and 61% of deionized water.
Adding 3ml of deionized water into a beaker, adding 1.5 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 30 percent of methacryloyl ethyl sulfobetaine, 5 percent of hydroxyethyl acrylate and 0.5 percent of ethylene glycol dimethacrylate into the solution, then adding 1 percent of initiator ammonium persulfate, adding 1 percent of reducing agent sodium bisulfite after 5-10 minutes, and transferring the mixture into a glass mold after the complete dissolution to polymerize for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
Example 7
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 35%;
1% of hydroxyethyl acrylate;
ethylene glycol dimethacrylate 3%;
1% of ammonium persulfate;
1% of sodium bisulfite;
2% of hectorite;
and 57% of deionized water.
Adding 3ml of deionized water into a beaker, adding 2 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 35 percent of methacryloyl ethyl sulfobetaine, 1 percent of hydroxyethyl acrylate and 3 percent of ethylene glycol dimethacrylate into the solution, then adding 1 percent of initiator ammonium persulfate, adding 1 percent of reducing agent sodium bisulfite after 5-10 minutes, transferring the mixture into a glass mold after the initiator ammonium persulfate is completely dissolved, and polymerizing for 24 hours at 25 ℃ to obtain the hydrogel type zwitterion medical adhesive.
Example 8
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 35%;
2% of hydroxyethyl acrylate;
ethylene glycol dimethacrylate 2%;
0.5 percent of ammonium persulfate;
0.5 percent of sodium bisulfite;
1.5 percent of hectorite;
and 58.5 percent of deionized water.
Adding 3ml of deionized water into a beaker, adding 1.5 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 35 percent of methacryloyl ethyl sulfobetaine, 2 percent of hydroxyethyl acrylate and 2 percent of ethylene glycol dimethacrylate into the solution, then adding 0.5 percent of initiator ammonium persulfate, adding 0.5 percent of reducing agent sodium bisulfite after 5-10 minutes, transferring the mixture into a glass mold after the initiator ammonium persulfate is completely dissolved, and polymerizing for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
Example 9
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 35%;
1% of hydroxyethyl acrylate;
ethylene glycol dimethacrylate 3%;
0.5 percent of ammonium persulfate;
0.5 percent of sodium bisulfite;
1% of hectorite;
and 59% of deionized water.
Adding 3ml of deionized water into a beaker, adding 1 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 35 percent of methacryloyl ethyl sulfobetaine, 1 percent of hydroxyethyl acrylate and 3 percent of ethylene glycol dimethacrylate into the solution, then adding 0.5 percent of initiator ammonium persulfate, adding 0.5 percent of reducing agent sodium bisulfite after 5-10 minutes, transferring the mixture into a glass mold after the complete dissolution, and polymerizing for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
Example 10
The reusable zwitterionic medical adhesive comprises the following components in percentage by weight:
methacryloylethyl sulfobetaine 40%;
0.5 percent of hydroxyethyl acrylate;
ethylene glycol dimethacrylate 3.5%;
1% of ammonium persulfate;
1% of sodium bisulfite;
1.5 percent of hectorite;
and 52.5 percent of deionized water.
Adding 3ml of deionized water into a beaker, adding 1.5 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 40 percent of methacryloyl ethyl sulfobetaine, 0.5 percent of hydroxyethyl acrylate and 3.5 percent of ethylene glycol dimethacrylate into the solution, then adding 1 percent of initiator ammonium persulfate, adding 1 percent of reducing agent sodium bisulfite after 5-10 minutes, transferring the mixture into a glass mold after the complete dissolution, and polymerizing for 24 hours at 25 ℃ to obtain the hydrogel type zwitterionic medical adhesive.
The zwitterionic medical adhesives prepared in examples 6-10 were characterized for peel strength, repeated peel, cytotoxicity, and fluid absorption, and are shown in Table 2 and FIG. 2.
Table 2 shows the properties of the zwitterionic medical adhesives prepared in examples 6 to 10
Figure DEST_PATH_IMAGE004
As can be seen from Table 2, by varying the concentration of the various components in the hydrogel, the various properties of the zwitterionic medical adhesive can be effectively varied. The zwitterionic medical adhesive prepared under the experimental conditions of the invention has the advantages of high adhesive strength, good repeated stripping performance, good absorption capacity to body fluid and no cytotoxicity, and can meet the requirements of practical application.
Comparative example 1
Methacryloylethyl sulfobetaine 39%;
0.5 percent of potassium persulfate;
0.5 percent of tetramethyl ethylene diamine;
1.5 percent of hectorite;
and 58.5 percent of deionized water.
Adding 3ml of deionized water into a beaker, adding 1.5 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 39 percent of methacryloyl ethyl sulfobetaine into the solution, then adding 0.5 percent of initiator potassium persulfate, adding 0.5 percent of reducer tetramethyl ethylenediamine after 5-10 minutes, transferring the mixture into a glass mold after the mixture is completely dissolved, and polymerizing for 24 hours at 25 ℃ to obtain the hydrogel type adhesive.
Comparative example 2
Methacryloylethyl sulfobetaine 39%;
0.5 percent of ammonium persulfate;
0.5 percent of sodium bisulfite;
1.5 percent of hectorite;
and 58.5 percent of deionized water.
Adding 3ml of deionized water into a beaker, adding 1.5 percent of hectorite, magnetically stirring at 0 ℃ until the hectorite is completely dissolved, then sequentially adding 39 percent of methacryloyl ethyl sulfobetaine into the solution, then adding 0.5 percent of initiator ammonium persulfate, adding 0.5 percent of reducing agent sodium bisulfite after 5-10 minutes, transferring the solution into a glass mold after the complete dissolution, and polymerizing for 24 hours at 25 ℃ to obtain the hydrogel type adhesive.
The zwitterionic medical adhesives prepared in control examples 1-2 were characterized and the results are shown in Table 3.
Table 3 shows the properties of the zwitterionic medical adhesives obtained in comparative examples 1-2
Figure DEST_PATH_IMAGE006
As can be seen from table 3, the zwitterionic medical adhesive obtained by polymerizing the zwitterionic monomer methacrylethyl sulfobetaine alone is not cytotoxic, but has poor adhesive strength and reusability, and too high body fluid absorption rate can cause excessive swelling of the adhesive, thus affecting tissue repair, and cannot be put into practical use, so that other functional monomers need to be introduced to improve the performance.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.

Claims (8)

1. The reusable zwitterionic medical adhesive is characterized by comprising the following components in percentage by mass
30-40% of zwitterionic monomer;
1.5 to 5 percent of functional monomer;
2.5 to 5 percent of functional monomer;
0.5 to 2 percent of initiator;
0.5 to 2 percent of cross-linking agent;
the balance of deionized water;
the functional monomer 1 is one of hydroxyethyl methacrylate, hydroxyethyl acrylate and N-isopropyl acrylamide;
the functional monomer 2 is one of triethylene glycol dimethacrylate, 1-vinyl imidazole or ethylene glycol dimethacrylate.
2. The reusable zwitterionic medical adhesive according to claim 1, wherein the zwitterionic monomer is a compound with a dipolar ion with positive and negative charges and is electrically neutral.
3. The reusable zwitterionic medical adhesive according to claim 2, wherein the zwitterionic monomer is methacrylethyl sulfobetaine.
4. The reusable zwitterionic medical adhesive according to claim 1, wherein the initiator is a redox initiator.
5. The reusable zwitterionic medical adhesive according to claim 4, wherein the oxidant in the initiator is one of potassium persulfate, ammonium persulfate and cumene hydroperoxide; the reducing agent in the initiator is one of sodium bisulfite, tetramethyl ethylenediamine and ferrous chloride.
6. The reusable zwitterionic medical adhesive according to claim 1, characterised in that the cross-linking agent is laponite.
7. A method of making the reusable zwitterionic medical adhesive according to any one of claims 1 to 6 characterised in that it includes the steps of:
s01, dispersing the cross-linking agent in deionized water at constant temperature until the cross-linking agent is completely dissolved;
s02, sequentially adding a zwitterion monomer into the solution obtained in the step S01, and obtaining a mixed solution by using a functional monomer 1 and a functional monomer 2;
s03, adding an oxidant in an initiator into the mixed solution obtained in the step S02, and adding a reducing agent after 5-10 minutes;
and S04, transferring the solution obtained in the step S03 to a glass mold for reaction to obtain a finished adhesive product.
8. The method for preparing the reusable zwitterionic medical adhesive according to claim 7, wherein the constant temperature in the step S01 is 0-20 ℃, the reaction temperature in the step S04 is 10-25 ℃, and the reaction time is 18-36 hours.
CN202210298700.8A 2022-03-25 2022-03-25 Reusable zwitterion medical adhesive and preparation method thereof Active CN114456309B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210298700.8A CN114456309B (en) 2022-03-25 2022-03-25 Reusable zwitterion medical adhesive and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210298700.8A CN114456309B (en) 2022-03-25 2022-03-25 Reusable zwitterion medical adhesive and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114456309A CN114456309A (en) 2022-05-10
CN114456309B true CN114456309B (en) 2023-02-28

Family

ID=81417451

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210298700.8A Active CN114456309B (en) 2022-03-25 2022-03-25 Reusable zwitterion medical adhesive and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114456309B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497208B (en) * 2014-12-12 2017-01-25 华南理工大学 Self-healing sulfobetaine zwitterionic nano composite aquagel and preparation method thereof
US20200246466A1 (en) * 2019-02-04 2020-08-06 Colorado School Of Mines Zwitterionic gels and methods of making the same
CN114106232B (en) * 2021-11-25 2022-08-30 华南农业大学 Hydrogel with different two-sided adhesiveness and preparation method and application thereof

Also Published As

Publication number Publication date
CN114456309A (en) 2022-05-10

Similar Documents

Publication Publication Date Title
CN110240712A (en) The high stretching of tissue adhesion a kind of, high viscosity, self-healing double-network hydrogel and its preparation method and application
CN113292671B (en) High molecular cross-linking agent containing phenylboronic acid group, biological adhesive prepared from high molecular cross-linking agent, preparation method and application of biological adhesive
Pourjavadi et al. Highly stretchable, self‐adhesive, and self‐healable double network hydrogel based on alginate/polyacrylamide with tunable mechanical properties
US11441120B2 (en) Cell culture substrate
JP2006500433A (en) Adhesive composition for wet media based on block copolymers containing at least one hydrophilic block
CN108047465A (en) A kind of methacrylate gelatin/chitosan interpenetration network hydrogel, preparation method and application
CN114173832A (en) Dry two-sided material for bonding wet tissue and devices
CN111234268A (en) Multifunctional specific biological adhesive hydrogel, preparation method and application thereof
CN114106232B (en) Hydrogel with different two-sided adhesiveness and preparation method and application thereof
CN113952500B (en) Tissue adhesive patch with single-sided adhesion and preparation method thereof
CN110894301B (en) Biodegradable natural polymer-based high-strength hydrogel and preparation method thereof
Aranaz et al. Pseudo-double network hydrogels with unique properties as supports for cell manipulation
CN114736397A (en) Preparation method and application of wet adhesive hydrogel for dura mater injury repair
CN108484936A (en) A kind of hydrogel and its preparation method and application prepared by graft modification material
CN114349996A (en) Super-smooth material and preparation method and application thereof
Yin et al. Photoinitiator-grafted polymer chains for integrating hydrogels with various materials
CN110144183B (en) Hydrogel adhesive capable of being used repeatedly and not damaging surface of base material, and preparation and application thereof
CN109824885B (en) Cysteine modified mussel bionic tissue adhesive and preparation method thereof
CN115040686A (en) Tissue adhesive film and preparation method thereof
CN114456309B (en) Reusable zwitterion medical adhesive and preparation method thereof
CN108409925A (en) A kind of Organic-inorganic covalent cross-linked hydrogel and preparation method thereof
JP2006271252A (en) Substrate for cell culture and method for cell culture
CN113577370B (en) Janus hydrogel adhesive and preparation method and application thereof
CN113817114A (en) Hydrogel, method for producing same, and medical material
CN114404643A (en) Tannin in-situ modified zwitterionic polymer medical adhesive and preparation method thereof

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