CN113929910B - Hyperbranched polymer underwater adhesive based on polyfunctional group rigid hydrophobic component and preparation method and application thereof - Google Patents
Hyperbranched polymer underwater adhesive based on polyfunctional group rigid hydrophobic component and preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a hyperbranched polymer underwater adhesive based on a polyfunctional group rigid hydrophobic component and a preparation method and application thereof, wherein the underwater adhesive is a hyperbranched polymer and an assembly thereof, the hyperbranched polymer takes polyfunctional group rigid molecules as the hydrophobic component and takes two adhesion groups of catechol and/or N-hydroxysuccinimide ester groups as side groups; the hyperbranched polymer assembly is formed by the conformation change of the hyperbranched polymer in a poor organic solvent and slight aggregation of rigid hydrophobic components. The adhesive disclosed by the invention can be adhered when meeting water, a coacervate is formed in 10s, no oxidant is needed to be added, the curing speed is high, the adhesion strength of the adhesive to ceramics and glass after being adhered and soaked underwater for 3 days can reach 1.1MPa, and the underwater strong adhesion to the base materials such as ceramics, glass, polymethyl methacrylate, polyethylene terephthalate, polyethylene, polytetrafluoroethylene and metal and the adhesion to various biological tissues in various water environments can be realized.
Description
Technical Field
The invention relates to the field of underwater adhesives and tissue adhesives, in particular to a water-triggered hyperbranched polymer underwater adhesive based on a polyfunctional group rigid hydrophobic component, and a preparation method and application thereof.
Background
Underwater adhesives have a wide range of uses such as attaching sensors, beacons or ammunition underwater, preventing water leakage, and medically repairing wet living tissue. However, common commercial adhesives such as cyanoacrylate and polyurethane have strong adhesion in air, and rapidly lose adhesion when contacting water, and cannot be used underwater. In aqueous environments, the presence of a hydrated water film on the substrate surface lowers the substrate surface energy and prevents direct chemical contact with the adhesive, thus achieving strong adhesion underwater remains a technical challenge.
Inspired by marine mussels, scientists have reported a large number of dopamine-based underwater adhesives. Catechol groups in dopamine can realize strong underwater adhesion to various substrates through hydrogen bonds, hydrophobic interaction, non-covalent interaction such as cation-pi, pi-pi and the like and covalent interaction such as metal chelation, boron-catechol complexation, coupling reaction, michael addition or Schiff base reaction and the like. However, the mussel-like underwater adhesive developed at present still has defects, such as: 1) The use of an oxidizing agent is required; 2) Long curing time, such as 7 days for epoxy resin adhesive; 3) The adhesive adheres to high surface energy substrates (such as ceramic, glass, PET, metal, PMMA, etc.) with adhesive strength greatly reduced to below 500kPa when used underwater compared with when used in air; 4) Cannot be used underwater for a long time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hyperbranched polymer underwater adhesive based on a polyfunctional group rigid hydrophobic component, a preparation method and application thereof.
In order to achieve the above object, one of the technical solutions of the present invention is:
a hyperbranched polymer underwater adhesive based on a polyfunctional group rigid hydrophobic component is a hyperbranched polymer and an assembly thereof, wherein the hyperbranched polymer takes polyfunctional group rigid molecules as the hydrophobic component and takes two adhesive groups of catechol and/or N-hydroxysuccinimide ester group as side groups; the hyperbranched polymer assembly is formed by the conformation change of the hyperbranched polymer in a poor organic solvent and slight aggregation of rigid hydrophobic components.
Further, the structure of the multifunctional rigid molecule is at least one of the following structures; wherein, (1) is 2,4, 6-triacrylate-1, 3, 5-triazine; (2) tetra-acrylamide tetraphenylethylene; (3) is octaacrylate cage type silsesquioxane;
the poor organic solvent is at least one of dichloromethane, trichloromethane, ethanol, propanol, acetone, acetonitrile and n-hexane.
One of the technical schemes of the invention is as follows: a preparation method of a hyperbranched polymer underwater adhesive is disclosed, wherein the hyperbranched polymer is prepared by carrying out Michael addition reaction on polyfunctional rigid molecules and dopamine hydrochloride under an alkaline condition.
The method specifically comprises the following steps:
(1) Putting polyfunctional group rigid molecules and dopamine hydrochloride into a round-bottom flask, dissolving the polyfunctional group rigid molecules and dopamine hydrochloride in dimethyl sulfoxide, stirring the solution until the solution is clear, and adjusting the pH value of the solution to 7.5-12;
(2) Placing the solution in an oil bath and stirring the solution in the dark place for reaction;
(3) After the reaction is finished, carrying out suction filtration to obtain a transparent solution, purifying the transparent solution by using methyl tert-butyl ether as a precipitator for several times to obtain a hyperbranched polymer;
(4) The residual precipitant was evacuated in a vacuum desiccator.
Further, the preparation method of the hyperbranched polymer underwater adhesive further comprises the step of adding a diacrylylation micromolecule, and carrying out Michael addition reaction on the diacrylylation micromolecule, a polyfunctional group rigid molecule and dopamine hydrochloride under an alkaline condition to obtain the hyperbranched polymer underwater adhesive; the method specifically comprises the following steps:
(1) Putting multifunctional group rigid molecules, diacryloylated micromolecules and dopamine hydrochloride into a round-bottom flask, dissolving by using dimethyl sulfoxide, stirring until the solution is clear, and adjusting the pH value of the solution to 7.5-12;
(2) Placing the solution in an oil bath and stirring the solution in the dark place for reaction;
(3) After the reaction is finished, carrying out suction filtration to obtain a transparent solution, purifying the transparent solution by using methyl tert-butyl ether as a precipitator for several times to obtain a hyperbranched polymer;
(4) Pumping out the residual precipitant in a vacuum drier;
the structure of the double-acryloyl small molecule is at least one of the following four structures:
Further, the preparation method of the hyperbranched polymer underwater adhesive further comprises the step of adding acrylic acid-N-succinimidyl ester, and carrying out Michael addition reaction on the acrylic acid-N-succinimidyl ester, polyfunctional rigid molecules, diacryloylated small molecules and dopamine hydrochloride under an alkaline condition to obtain the hyperbranched polymer underwater adhesive; the method specifically comprises the following steps:
(1) Putting multifunctional group rigid molecules, diacrylylation micromolecules, dopamine hydrochloride and acrylic acid-N-succinimidyl ester into a round-bottom flask, dissolving by using dimethyl sulfoxide, stirring until the solution is clear, and adjusting the pH value of the solution to 7.5-12;
(2) Placing the solution in an oil bath and stirring the solution in the dark place for reaction;
(3) After the reaction is finished, carrying out suction filtration to obtain a transparent solution, purifying the transparent solution by using methyl tert-butyl ether as a precipitator for several times to obtain a hyperbranched polymer;
(4) The residual precipitant was evacuated in a vacuum desiccator.
One of the technical schemes of the invention is as follows: a preparation method of a hyperbranched polymer underwater adhesive is realized by utilizing a solution self-assembly strategy, wherein a hyperbranched polymer is dispersed in a poor organic solvent of polyfunctional rigid molecules in a purification process to induce the self-assembly of the hyperbranched polymer, and finally, the hyperbranched polymer is precipitated and purified in methyl tert-butyl ether and is repeated for a plurality of times to obtain the hyperbranched polymer assembly with rigid hydrophobic components gathered; the method specifically comprises the following steps: purifying the transparent solution obtained in any step (3) by using methyl tert-butyl ether as a precipitator, dispersing the obtained precipitate in a poor organic solvent of polyfunctional rigid molecules, and finally precipitating in the methyl tert-butyl ether for several times to obtain a hyperbranched polymer assembly; the residual poor organic solvent and precipitant were removed in a vacuum desiccator.
Further, the double bond molar ratio of the multifunctional rigid molecule to the double-acryloyl small molecule is (0.5-2): 1.
The molar ratio of the double bonds to the amino groups in the multifunctional rigid molecule, the diacrylylated small molecule and the dopamine hydrochloride is (1.7-2): 1, preferably (1.8-2): 1.
The mass ratio of the solvent dimethyl sulfoxide to the hydrochloric acid dopamine is (6.5-15) to 1.
The number of double bonds of the multifunctional rigid molecule, the number of double bonds of the bisacryloyl micromolecule, the number of double bonds of acrylic acid-N-succinimide ester = (4-16), 8 (1-4), preferably 8.
Preferably, the pH of the solution is adjusted to 7.5-8.5.
The reaction temperature is 40-80 ℃, and the reaction time is 0.5-10h, preferably 0.5-3h.
The amount of the methyl tert-butyl ether is 5-10 times of the volume of the solution to be purified, and the purification times are 3-6 times.
The amount of poor organic solvent for the multifunctional rigid molecule is 0.5-1 times of the precipitation volume.
The time in the vacuum dryer is 12-48h.
One of the technical schemes of the invention is as follows: an application of the hyperbranched polymer underwater adhesive based on polyfunctional group rigid hydrophobic component in adhesion under water, air and different humidity conditions and biological tissue adhesion.
Further, the application of the method to underwater adhesion comprises preparing adhesion samples in deionized water, PBS solution, artificial seawater and solutions with different pH values; the adhesive is applied to adhesion in air, triggered to coagulate by water spraying or soaking water, adhered in air to prepare a sample, and placed in air or soaked in deionized water, PBS solution, artificial seawater and solutions with different pH values; applying to the different humidity conditions an adherence comprising 0-100% RH; the adhesive is applied to biological tissue adhesion, and is coated on the surface of the biological tissue and is triggered to coagulate by spraying water or soaking water for adhesion, or is coated on the surface of the biological tissue for adhesion after being triggered to coagulate by spraying water or soaking water.
The invention has the beneficial effects that:
(1) The hyperbranched polymer underwater adhesive is synthesized by adopting one-step Michael addition reaction, and the preparation process is simple and easy to implement.
(2) The hyperbranched polymer underwater adhesive has a unique highly branched three-dimensional structure: the adhesive comprises a polyfunctional group rigid hydrophobic inner core and dense catechol end groups, wherein after the adhesive is contacted with water, the rigid hydrophobic component shrinks and aggregates, the catechol group is exposed and aggregates outwards, and a hydrated water layer at the interface of a substrate and the adhesive is damaged, so that the substrate and the adhesive are in close contact. The hyperbranched polymer underwater adhesive can realize strong underwater adhesion without being triggered by external conditions such as temperature, pH and the like due to the self-condensation property when meeting water.
(3) The hyperbranched polymer underwater adhesive improves the adhesive property and the degradation property of the underwater adhesive by optimizing the molecular weight, the hydrophilicity and the hydrophobicity and the variety of functional groups of the diacrylylation micromolecules. Hyperbranched polymers with suitable hydrophobicity and suitable catechol group density show the most excellent underwater adhesion properties. For example, when the diacrylated small molecule is polyethylene glycol diacrylate (average molecular weight 400), polyethylene glycol diacrylate (average molecular weight 308), polyethylene glycol diacrylate (average molecular weight 200), 1, 4-butanediol diacrylate (molecular weight 198) and 1, 6-hexanediol diacrylate (molecular weight 226), the adhesive strength of the hyperbranched polymer is increased along with the increase of hydrophobicity and catechol group density, and the adhesive strength of the hyperbranched polymer is highest when the diacrylated small molecule is 1, 4-butanediol diacrylate (molecular weight 198). When the diacrylation small molecule is 1, 6-hexanediol diacrylate (molecular weight 226), the hydrophobicity is further increased but the catechol group density is reduced, resulting in slightly reduced adhesive strength of the hyperbranched polymer, but still having better adhesive strength. The hyperbranched polymer also has degradation responsiveness when the diacrylylated small molecule is N, N' -bis (acryloyl) cystamine.
(4) The hyperbranched polymer underwater adhesive disclosed by the invention is adhered when meeting water, a coacervate is formed in 10s, no oxidant is needed to be added, the curing speed is high, the adhesive strength of the hyperbranched polymer underwater adhesive to ceramics and glass after being adhered and soaked for 3 days under water can reach 1.1MPa, and the hyperbranched polymer underwater adhesive can realize the underwater strong adhesion to the base materials such as ceramics, glass, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene (PE), polytetrafluoroethylene (PTFE), metal and the like and the adhesion to various biological tissues in various water environments.
(5) According to the hyperbranched polymer underwater adhesive, poor solvent such as dichloromethane of polyfunctional rigid molecules is introduced in the purification process, so that the polymer molecules can be promoted to aggregate, and an assembly with more excellent underwater adhesion performance is obtained; in the reaction process, acrylic acid-N-succinimide ester is added, and succinimide groups are introduced on the hyperbranched polymer, so that the succinimide ester can form chemical bonds with amino groups on tissues when being applied to tissue adhesion, and is more favorable for adhesion to biological tissues.
(6) The hyperbranched polymer underwater adhesive has water resistance, repeated adhesion and long-term strong adhesion.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 2,4, 6-triacrylate-1, 3, 5-triazine product obtained by the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of a tetra-acrylamide tetraphenylethylene product prepared by the present invention.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the product obtained in example 2 of the present invention.
FIG. 4 is the underwater adhesion strength to various substrates (A) and the repetitive adhesion strength to PE (B) of the rigid component aggregated hyperbranched polymer assembly of example 2 of the invention.
FIG. 5 is water resistant adhesive strength (A) and repeated adhesive strength (B) to ceramic of hyperbranched polymer assemblies with aggregated rigid components of example 2 of the present invention to various substrates.
FIG. 6 is the lap shear curve (A) and adhesion strength (B) of the rigid component aggregated hyperbranched polymer assembly of example 2 of the invention as a tissue adhesive, adhering to pigskin.
FIG. 7 is a nuclear magnetic hydrogen spectrum of a product obtained in example 3 of the present invention.
FIG. 8 shows the lap shear curve (A) and adhesion strength (B) of the porcine skin adhered with the modified succinimide group hyperbranched polymer of example 3 of the present invention as a tissue adhesive.
FIG. 9 is a graph showing the lap shear adhesion strength test of the modified succinimide group-modified hyperbranched polymer of example 3 of the present invention after adhering to a pigskin (A), and a schematic view showing that the polymer bears a load of 1kg after adhering to the pigskin (B).
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention, but the examples are not intended to limit the scope of the present invention. Unless otherwise specified, the starting materials used in the examples of the present invention are commercially available, with the octaacrylate cage silsesquioxanes being available from Hybrid Plastics (Hatties burg, MS).
The preparation method of 2,4, 6-triacrylate-1, 3, 5-triazine is as follows:
(1) Weighing 30mL of dimethyl sulfoxide into a 250mL round-bottom flask, placing the round-bottom flask into a normal-temperature water bath, stirring, sequentially weighing 0.4414g of melamine and 0.0397g of p-hydroxyanisole (polymerization inhibitor), putting the melamine and the p-hydroxyanisole into the round-bottom flask, and stirring until the mixture is clear.
(2) 1815. Mu.L of acrylic anhydride was measured, diluted with 10mL of dimethyl sulfoxide, placed in an isobaric dropping funnel, the piston of the isobaric dropping funnel was adjusted to start dropping slowly into the round-bottom flask and to start timing, and the reaction was stopped after stirring for 3 hours.
(3) After the reaction is finished, a yellow transparent solution V is obtained 0 And (mL). Ten-fold methyl tert-butyl ether (10V) was used 0 mL) purified clear solution: measuring 10V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magnetic seed at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 mL; purification was repeated three times to obtain 2,4, 6-triacrylate-1, 3, 5-triazine.
(4) The residual methyl tert-butyl ether was removed in a vacuum desiccator by pumping for 24 h. The nuclear magnetic hydrogen spectrum of the obtained 2,4, 6-triacrylate-1, 3, 5-triazine is shown in FIG. 1. The results prove that the 2,4, 6-triacrylate-1, 3, 5-triazine of the invention is successfully prepared.
The proportion standard of the raw materials is that the mol ratio of amino to acrylic anhydride in the melamine is 1.5, and the mass of the p-hydroxyanisole is 2 percent of the mass of the acrylic anhydride.
Tetraacrylamide tetraphenylethylene was prepared as above, except that melamine was replaced with tetrakis- (4-aminophenyl) ethylene. The nuclear magnetic hydrogen spectrum of the tetra-acrylamide tetraphenylethylene is shown in figure 2. The results prove that the tetra-acrylamide tetraphenylethylene is successfully prepared.
Bis-acryloylated small molecules
The preparation method comprises the following steps:
(1) 2-hydroxyethyl vinyl ether (26.4 g,0.3 mol) and Triethylamine (TEA) (33.3 g, 0.33mol) were dissolved in 250mL of anhydrous Dichloromethane (DCM), and acryloyl chloride (30g, 0.33mol) was added dropwise while cooling on ice, and then allowed to warm to room temperature naturally for overnight reaction. Filtering to remove precipitate, washing the filtrate with water for three times, and adding anhydrous MgSO 4 Drying, removal of the solvent and drying in vacuo gave the product VEA as a colorless liquid in 94% yield.
(2) 2-hydroxyethyl acrylate (38g, 0.33mol) and pyridine p-toluenesulfonate (PPTS) (678mg, 2.7 mmol) were dissolved in 200mL of anhydrous DCM in an ice bath, N 2 50mL of anhydrous DCM containing VEA (38.3 g, 0.27mol) were added dropwise with protection, and then allowed to spontaneously rise to room temperature for 3h. Adding a proper amount of K 2 CO 3 The reaction was terminated and after stirring for a period of time filtered through a G5 sand funnel with celite. The filtrate was collected, rotovaped to remove solvent and volatiles and purified by silica gel column chromatography (eluent: ethyl acetate: n-hexane =1:50 plus 1% tea) and dried in vacuo to give a colorless liquid as the product in 82% yield.
The preparation process of the adhesive sample when the supramolecular polymer underwater adhesive is applied to underwater adhesion, water-resistant adhesion and biological tissue adhesion is as follows:
(1) Underwater adhesion: the whole process is carried out in deionized water. The adhesive was applied uniformly under water to the surface of one substrate and then bonded to the other substrate, and the bonded area was pressed with a 1kg weight for 10min, and after soaking in water for various periods, the lap shear adhesion strength test was performed (substrate: ceramic, glass, PMMA, PET, PE, PTFE, fe; substrate size: about 2.5 cm. Times.7 cm; adhesive area: about 2.5 cm. Times.1 cm; amount of adhesive: about 30 mg).
(2) Water-resistant adhesion: the preparation process of the adhesion sample is carried out in air, and the sample is soaked in water after being prepared. The adhesive is uniformly coated on the surface of one substrate in the air, then the substrate is contacted with the other substrate, the adhesive is uniformly coated on the other substrate, the adhesive is triggered to be condensed by spraying water or soaking water, the two substrates are bonded together in the air, the air and the water at the interface are removed, the bonding area is pressed for 10min by using a weight of 1kg, and then the substrate is soaked in the water for different time periods to carry out the lap shear bonding strength test (the substrates are ceramics, glass, PMMA, PET, PE, PTFE and Fe, the size of the substrate is about 2.5cm multiplied by 7cm, the bonding area is about 2.5cm multiplied by 1cm, and the dosage of the adhesive is about 12 mg).
(3) Biological tissue adhesion: firstly, coating an adhesive on the outer surface of a base material, and carrying out bonding by triggering coagulation through water spraying or soaking water, or coating the adhesive on the surface of a tissue to bond after triggering coagulation through water spraying or soaking water, then covering the outer surface of the other base material on an area coated with the adhesive, and pressing for bonding (base material: pigskin).
The lap shear adhesion strength of the supramolecular polymer underwater adhesive to the substrate was tested as follows: the lap shear adhesion strength was tested using an electronic universal tester (UTM model 6104) with a 500N sensor for underwater adhesion, biological tissue adhesion and a 10KN sensor for water-resistant adhesion. Use slide caliper to measure and record adhesion zone area S before the test, then fix the sample that awaits measuring on two tensile anchor clamps about, use with the sample that awaits measuring and guarantee that thickness is unanimous about the gasket of the same material with thickness, zero load and stretch the sample with 5 mm/min' S tensile rate, record the maximum force F among the tensile process, record adhesion failure mode: cohesive failure, interfacial failure, substrate failure. The lap shear adhesion strength can be calculated according to the following formula (1). At least four replicates of each substrate were tested and the results averaged.
Adhesion Strength = F/S (1)
Example 1
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 3.304g of octaacrylate polyhedral oligomeric silsesquioxane, 3.08g of polyethylene glycol diacrylate (average molecular weight 308) and 4.335g of dopamine hydrochloride are weighed into a 250mL round-bottom flask, dissolved with 50mL of dimethyl sulfoxide and stirred until clear, and then 4.5mL of triethylamine is added to adjust the pH of the solution to 8.0.
(2) The solution is placed in an oil bath at 40 ℃ and stirred for reaction for 3 hours in a dark place.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, then purify the clear solution three times using tert-butyl methyl ether penta: the first time of measuring 5V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magnetic seed at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 And (mL). The quintupling methyl tert-butyl ether (5V) is taken out for the second time 1 mL), separating with a centrifuge and decanting the supernatant to give precipitate V 2 And (mL). The quintupling methyl tert-butyl ether (5V) is taken out for the third time 2 mL), separating with a centrifuge and decanting the supernatant to obtain the hyperbranched polymer.
(4) The residual methyl t-butyl ether was removed by 24h in a vacuum desiccator to give 7.91g of product in 80% yield.
Example 2
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 0.3304g of octaacrylate polyhedral oligomeric silsesquioxane, 0.198g of 1, 4-butanediol diacrylate and 0.3793g of dopamine hydrochloride were weighed into a 50mL round-bottomed flask, dissolved in 5mL of dimethyl sulfoxide and stirred until clear, and then 400. Mu.L of triethylamine was added to adjust the pH of the solution to 8.0.
(2) The solution is put in an oil bath at 80 ℃ and stirred for reaction for 1h in the dark.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, first using quintuplinyl methyl tert-butyl ether (5V) 0 mL) purified clear solution: measuring 5V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magneton at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 mL; second addition of V 1 The precipitate was dissolved in mL of dichloromethane and was purified with tert-butyl methyl ether (10V) 1 mL), separating by using a centrifuge and pouring out supernatant to obtain precipitate; repeating the second purification process twice for four times to obtain the hyperbranched polymer assembly with the aggregated rigid components.
(4) Residual methylene chloride and methyl tert-butyl ether were removed by evacuation in a vacuum desiccator for 24h to give 0.71g of product in 85% yield.
The nuclear magnetic hydrogen spectrum of the hyperbranched polymer assembly obtained in example 2 is shown in fig. 3. As can be seen from FIG. 3, at 5.8-6.4ppm, the proton peak of the double bond disappeared, and the peak of the benzene ring appeared at 6.43-6.62ppm, indicating that the catechol group was successfully grafted to the end of the double bond by Michael addition reaction, and the hyperbranched polymer assembly was successfully prepared.
The underwater adhesion strength of the hyperbranched polymer assembly obtained in example 2 to different substrates (soaked in deionized water for 72 h) is shown in fig. 4A, and the adhesion strength to ceramic, glass, PMMA, PET, PE, PTFE and steel sheet is 1144, 1179, 810, 732, 340, 191 and 1124kPa respectively; repeated adhesion strength to PE as shown in fig. 4B, in a five consecutive cycles of lap shear testing, although the adhesion strength decreased to 0.43 times the initial adhesion strength at the second cycle, there was only a slight loss of adhesion strength in the subsequent cycles; the hyperbranched polymer assembly has wide underwater strong adhesion and certain repeated adhesion.
The water resistant adhesive strength (soaked in deionized water for 24 h) of the hyperbranched polymer assembly obtained in example 2 on different substrates is shown in fig. 5A, the adhesive strength on ceramic, glass, PMMA, PET, PE, PTFE and iron sheets is 1731, 2961, 1249, 2888, 550, 150 and 972kPa respectively, the repeated adhesive strength on ceramic is shown in fig. 5B, in a lap shear test of five consecutive cycles, although the adhesive strength decreases 0.33 times the initial adhesive strength at the second cycle, the adhesive strength is only slightly lost in the subsequent cycles, and the adhesive strength still remains 488kPa for the fifth cycle; the hyperbranched polymer underwater adhesive has wide water-resistant strong adhesion and certain repeated adhesion.
The lap shear curve of the hyperbranched polymer assembly obtained in example 2 on the pig skin (area of the adhesion area: 1.6 cm. Times.1 cm) after being left in air for 24 hours is shown in FIG. 6A, and the adhesion strength is 102kPa (FIG. 6B).
Example 3
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 3.304g of octaacrylate polyhedral oligomeric silsesquioxane, 2.604g of N, N' -bis (acryloyl) cystamine, 0.873g of acrylic acid-N-succinimidyl ester and 4.894g of dopamine hydrochloride were weighed into a 100mL round-bottomed flask, dissolved with 50mL of dimethyl sulfoxide and stirred until clear, and then 5.1mL of triethylamine was added to adjust the pH of the solution to 8.0.
(2) The solution is put in an oil bath at 80 ℃ and stirred for reaction for 1h in the dark.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, then purify the clear solution three times using tert-butyl methyl ether penta: first measuring 5V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magnetic seed at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 And (mL). The quintupling methyl tert-butyl ether (5V) is taken out for the second time 1 mL), separation using a centrifuge and decanting the supernatant to give precipitate V 2 And (mL). The quintupling methyl tert-butyl ether (5V) is taken out for the third time 2 mL), the precipitate was purified, separated using a centrifuge and the supernatant decanted to give a hyperbranched polymer modified with succinimide groups.
(4) The residual methyl t-butyl ether was removed by 24h in a vacuum desiccator to give 8.69g of product in 81% yield.
The nuclear magnetic hydrogen spectrum of the hyperbranched polymer obtained in example 3 is shown in FIG. 7. As can be seen from FIG. 7, at 5.8 to 6.4ppm, the proton peak of the double bond disappeared, and the peak of the benzene ring appeared at 6.43 to 6.62ppm, indicating that the catechol group was successfully grafted to the end of the double bond by the Michael addition reaction, and the hyperbranched polymer was successfully prepared.
The test chart of the lap shear adhesion strength of the modified succinimide group hyperbranched polymer obtained in example 3 after being adhered to a pigskin (adhering area: 1.5 cm. Times.1.5 cm) (left in air for 24 hours) is shown in FIG. 9A, the lap shear curve is shown in FIG. 8A, and the adhesion strength is 135kPa (FIG. 8B); FIG. 9B is a schematic view showing that a hyperbranched polymer modified with succinimide groups bears a load of 1kg after being adhered to pig skin (area of adhesion region: 1.0 cm. Times.1.5 cm); the hyperbranched polymer modified with the succinimide group has excellent adhesion effect on biological tissues, and provides a new idea for developing biological adhesives.
Example 4
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 0.6608g of octaacrylate polyhedral oligomeric silsesquioxane and 0.3793g of dopamine hydrochloride are weighed into a 50mL round-bottom flask, dissolved in 5mL of dimethyl sulfoxide and stirred until the solution is clear, and 400 μ L of triethylamine is added to adjust the pH of the solution to 8.0.
(2) The solution was stirred in an oil bath at 80 ℃ for 1h in the dark.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, then purify the clear solution three times using ten times methyl tert-butyl ether: first measuring 10V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magneton at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 And (mL). Taking ten times of methyl tert-butyl for the second timeEther (10V) 1 mL), separating with a centrifuge and decanting the supernatant to give precipitate V 2 And (mL). Ten-fold methyl tert-butyl ether (10V) is taken out for the third time 2 mL), separating with a centrifuge and decanting the supernatant to obtain the hyperbranched polymer.
(4) The residual methyl t-butyl ether was removed by 12h in a vacuum desiccator to give 0.67g of product in 70% yield.
Example 5
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 0.576g of 2,4, 6-triacrylate-1, 3, 5-triazine, 0.594g of 1, 4-butanediol diacrylate, 1.1378g of dopamine hydrochloride are weighed into a 50mL round-bottomed flask, dissolved in 14mL of dimethyl sulfoxide and stirred until clear, and 1.2mL of triethylamine are added to adjust the pH of the solution to 8.0.
(2) The solution is put in an oil bath at 80 ℃ and stirred for reaction for 1h in the dark.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, first using quintuplinyl methyl tert-butyl ether (5V) 0 mL) clear solution was purified: measuring 5V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magneton at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 mL; second addition of V 1 The precipitate was dissolved in mL of dichloromethane and was purified with tert-butyl methyl ether (10V) 1 mL), separating by using a centrifuge and pouring out supernatant to obtain precipitate; repeating the second purification process twice for four times to obtain the hyperbranched polymeric assembly with the aggregated rigid components.
(4) Residual dichloromethane and methyl tert-butyl ether were removed by 24h in a vacuum desiccator to give 1.71g of product in 82% yield.
Example 6
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 3.304g of octaacrylate cage-type silsesquioxane, 3.08g of polyethylene glycol diacrylate (average molecular weight 308) and 4.335g of dopamine hydrochloride are weighed into a 250mL round-bottom flask, dissolved in 50mL of dimethyl sulfoxide and stirred until clear, and then 4mL of triethylamine is added to adjust the pH of the solution to 8.0.
(2) The solution is placed in an oil bath at 40 ℃ and stirred for reaction for 3 hours in a dark place.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 And (mL). Pentafmedimethyl tert-butyl ether (5V) was used for the first time 0 mL) clear solution was purified: measuring 5V 0 Placing mL of methyl tert-butyl ether in a 600mL conical flask, stirring with a magneton at the bottom, adding the transparent solution dropwise into the conical flask with a pipette, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 mL; second addition of V 1 The precipitate was dissolved in mL of dichloromethane and was purified with tert-butyl methyl ether (10V) 1 mL), separating by using a centrifugal machine, and pouring out the supernatant to obtain a precipitate; repeating the second purification process twice for four times to obtain the intermolecular aggregated hyperbranched polymer assembly.
(4) Residual methylene chloride and methyl tert-butyl ether were removed by 24h in a vacuum desiccator to give 7.91g of product in 80% yield.
Example 7
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 0.288g of 2,4, 6-triacrylate-1, 3, 5-triazine, 0.3g of polyethylene glycol diacrylate (average molecular weight 200), and 0.5689g of dopamine hydrochloride were weighed into a 50mL round-bottomed flask, dissolved in 7mL of dimethyl sulfoxide and stirred until clear, and 600. Mu.L of triethylamine was added to adjust the pH of the solution to 8.0.
(2) The solution is put in an oil bath at 80 ℃ and stirred for reaction for 3 hours in a dark place.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, first use five times methyl tert-butyl ether (5V) 0 mL) purified thoroughlyClear solution: measuring 5V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magnetic seed at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 mL; second addition of V 1 The precipitate was dissolved in mL of dichloromethane and was treated with t-butyl methyl ether (10V) 1 mL), separating by using a centrifuge and pouring out supernatant to obtain precipitate; repeating the second purification process twice for four times to obtain the hyperbranched polymer assembly with the aggregated rigid components.
(4) Residual methylene chloride and methyl tert-butyl ether were removed by 24h in a vacuum desiccator to give 0.88g of the product in 84% yield.
Example 8
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 6.608g of octaacrylate polyhedral oligomeric silsesquioxane, 4.52g of 1, 6-hexanediol diacrylate and 7.586g of dopamine hydrochloride are weighed into a 250mL round-bottom flask, dissolved in 50mL of dimethyl sulfoxide and stirred until the solution is clear, and then 4mL of triethylamine is added to adjust the pH of the solution to 8.0.
(2) The solution is put in an oil bath at 40 ℃ and stirred for reaction for 1h in a dark place.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, then purify the clear solution three times using tert-butyl methyl ether penta: the first time of measuring 5V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magnetic seed at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 And (mL). The quintupling methyl tert-butyl ether (5V) is taken out for the second time 1 mL), separating with a centrifuge and decanting the supernatant to give precipitate V 2 And (mL). The quintupling methyl tert-butyl ether (5V) is taken out for the third time 2 mL), the precipitate was purified, separated using a centrifuge and the supernatant decanted to give the hyperbranched polymer.
(4) The residual methyl t-butyl ether was removed by 24h in a vacuum desiccator to give 12.94g of product in 75% yield.
Example 9
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 0.864g of 2,4, 6-triacrylate-1, 3, 5-triazine and 0.853g of dopamine hydrochloride are weighed into a 250mL round-bottomed flask, dissolved in 10mL of dimethyl sulfoxide and stirred until clear, and 900. Mu.l of triethylamine are added to adjust the pH of the solution to 8.0.
(2) The solution is placed in an oil bath at 80 ℃ and stirred for reaction for 3 hours in a dark place.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, then purify the clear solution three times using ten times methyl tert-butyl ether: first measuring 10V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magnetic seed at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 And (mL). Ten-fold methyl tert-butyl ether (10V) is measured out for the second time 1 mL), separation using a centrifuge and decanting the supernatant to give precipitate V 2 And (mL). Ten-fold methyl tert-butyl ether (10V) is taken out for the third time 2 mL), separating with a centrifuge and decanting the supernatant to obtain the hyperbranched polymer.
(4) The residual methyl tert-butyl ether was removed by 48h in a vacuum desiccator to give 1.21g of product in 78% yield.
Example 10
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 1.5311g tetraacrylamide tetraphenylethylene, 3.08g polyethylene glycol diacrylate (average molecular weight 308), 4.362g dopamine hydrochloride were weighed into a 250mL round bottom flask, dissolved with 50mL dimethylsulfoxide and stirred until clear, then 400. Mu.L triethylamine was added to adjust the pH of the solution to 8.0.
(2) The solution is put in an oil bath at 80 ℃ and stirred for reaction for 1h in the dark.
(3) The reaction is finishedThen, removing triethylamine hydrochloride generated in the reaction process by suction filtration to obtain a transparent solution V 0 mL, first using quintuplinyl methyl tert-butyl ether (5V) 0 mL) clear solution was purified: measuring 5V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magnetic seed at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 mL; second addition of V 1 The precipitate was dissolved in mL of dichloromethane and was purified with tert-butyl methyl ether (10V) 1 mL), separating by using a centrifuge and pouring out supernatant to obtain precipitate; and repeating the second purification process twice, and purifying for four times to obtain the hyperbranched polymer assembly with the aggregated rigid components.
(4) Residual methylene chloride and methyl t-butyl ether were removed by 24h in a vacuum desiccator to give 6.91g of product in 85% yield.
Example 11
A hyperbranched polymer underwater adhesive based on a multifunctional rigid hydrophobic component is prepared by the following steps:
(1) 0.3304g of octaacrylate cage-type silsesquioxane and 0.258g of the mixture were weighed out
0.3793g dopamine hydrochloride was put into a 50mL round bottom flask, dissolved in 5mL dimethyl sulfoxide and stirred until clear, then 400. Mu.L triethylamine was added to adjust the pH of the solution to 8.0.
(2) The solution is put in an oil bath at 80 ℃ and stirred for reaction for 1h in the dark.
(3) After the reaction is finished, removing triethylamine hydrochloride generated in the reaction process through suction filtration to obtain a transparent solution V 0 mL, first using quintuplinyl methyl tert-butyl ether (5V) 0 mL) purified clear solution: measuring 5V 0 Placing mL of methyl tert-butyl ether in a conical flask, stirring with a magnetic seed at the bottom, adding the transparent solution dropwise into the conical flask with a suction tube, separating with a centrifuge, and pouring off the supernatant to obtain precipitate V 1 mL; second addition of V 1 The precipitate was dissolved in mL of dichloromethane and was purified with tert-butyl methyl ether (10V) 1 mL) was continued to be pureDissolving, separating by using a centrifugal machine, and pouring out supernatant to obtain precipitate; repeating the second purification process twice for four times to obtain the hyperbranched polymer assembly with the aggregated rigid components.
(4) Residual methylene chloride and methyl tert-butyl ether were removed by evacuation in a vacuum desiccator for 24h to give 0.76g of product in 85% yield.
Claims (13)
1. The preparation method of the hyperbranched polymer underwater adhesive based on the multifunctional rigid hydrophobic component is characterized in that the underwater adhesive is a hyperbranched polymer or an assembly thereof, wherein the hyperbranched polymer takes multifunctional rigid molecules as the hydrophobic component and catechol adhesive groups as side groups; the hyperbranched polymer assembly is formed by slightly aggregating rigid hydrophobic components due to conformational change of the hyperbranched polymer in a poor organic solvent;
the structure of the multifunctional rigid molecule is at least one of the following structures; wherein (1) is 2,4, 6-triacrylate-1, 3, 5-triazine; (2) tetra-acrylamide tetraphenylethylene; (3) is octaacrylate cage type silsesquioxane;
the preparation method of the hyperbranched polymer is that the hyperbranched polymer is prepared by carrying out Michael addition reaction on polyfunctional group rigid molecules and dopamine hydrochloride under alkaline conditions.
2. The method of claim 1, wherein the poor organic solvent is at least one of dichloromethane, chloroform, ethanol, propanol, acetone, acetonitrile, and n-hexane.
3. The method for preparing the hyperbranched polymer underwater adhesive as claimed in claim 1, wherein the specific preparation method of the hyperbranched polymer comprises the following steps:
(1) Putting polyfunctional group rigid molecules and dopamine hydrochloride into a round-bottom flask, dissolving the polyfunctional group rigid molecules and dopamine hydrochloride in dimethyl sulfoxide, stirring the solution until the solution is clear, and adjusting the pH value of the solution to 7.5-12;
(2) Placing the solution in an oil bath and stirring the solution in the dark place for reaction;
(3) After the reaction is finished, carrying out suction filtration to obtain a transparent solution, and purifying the transparent solution for several times by using methyl tert-butyl ether as a precipitator to obtain a hyperbranched polymer;
(4) The residual precipitant was removed in a vacuum desiccator.
4. The method of preparing a hyperbranched polymeric underwater adhesive as claimed in claim 3,
the mass ratio of the solvent dimethyl sulfoxide to the dopamine hydrochloride is (6.5-15) to 1;
adjusting the pH value of the solution to 7.5-8.5;
the reaction temperature is 40-80 ℃, and the reaction time is 0.5-10h;
the using amount of the methyl tert-butyl ether is 5-10 times of the volume of the solution to be purified, and the purification times are 3-6 times;
the time in the vacuum dryer is 12-48h.
5. The method for preparing the underwater adhesive of the hyperbranched polymer as claimed in claim 1, wherein the method for preparing the hyperbranched polymer further comprises adding a diacrylation micromolecule to perform Michael addition reaction with a multifunctional rigid molecule and dopamine hydrochloride under alkaline conditions; the method specifically comprises the following steps:
(1) Putting multifunctional group rigid molecules, diacrylylation micromolecules and dopamine hydrochloride into a round-bottom flask, dissolving by using dimethyl sulfoxide, stirring until the solution is clear, and adjusting the pH value of the solution to 7.5-12;
(2) Placing the solution in an oil bath and stirring the solution in the dark place for reaction;
(3) After the reaction is finished, carrying out suction filtration to obtain a transparent solution, purifying the transparent solution by using methyl tert-butyl ether as a precipitator for several times to obtain a hyperbranched polymer;
(4) Pumping out the residual precipitant in a vacuum drier;
the structure of the double-acryloyl small molecule is at least one of the following four structures:
6. The method of preparing hyperbranched polymeric underwater adhesive of claim 5,
the double bond mol ratio of the multifunctional group rigid molecule to the double-acryloyl small molecule is (0.5-2) to 1;
the molar ratio of double bonds in the multifunctional rigid molecule and the diacrylylation micromolecule to amino groups in the dopamine hydrochloride is (1.7-2): 1;
the mass ratio of the solvent dimethyl sulfoxide to the hydrochloric acid dopamine is (6.5-15) to 1;
adjusting the pH of the solution to 7.5-8.5;
the reaction temperature is 40-80 ℃, and the reaction time is 0.5-10h;
the using amount of the methyl tert-butyl ether is 5-10 times of the volume of the solution to be purified, and the purification times are 3-6 times;
the time in the vacuum drier is 12-48h.
7. The method for preparing the underwater adhesive of the hyperbranched polymer as claimed in claim 5, wherein the method for preparing the hyperbranched polymer further comprises adding acrylic acid-N-succinimide ester to perform Michael addition reaction with the multifunctional rigid molecule, the diacrylylated small molecule and dopamine hydrochloride under alkaline conditions; the method specifically comprises the following steps:
(1) Putting multifunctional group rigid molecules, diacryloylated micromolecules, dopamine hydrochloride and acrylic acid-N-succinimidyl ester into a round-bottom flask, dissolving by using dimethyl sulfoxide, stirring until the solution is clear, and adjusting the pH value of the solution to 7.5-12;
(2) Placing the solution in an oil bath and stirring the solution in the dark place for reaction;
(3) After the reaction is finished, carrying out suction filtration to obtain a transparent solution, purifying the transparent solution by using methyl tert-butyl ether as a precipitator for several times to obtain a hyperbranched polymer;
(4) The residual precipitant was evacuated in a vacuum desiccator.
8. The method of preparing a hyperbranched polymeric underwater adhesive as claimed in claim 7,
the double bond mol ratio of the multifunctional group rigid molecule to the double-acryloyl small molecule is (0.5-2) to 1;
the molar ratio of double bonds in the multifunctional rigid molecule and the diacrylylation micromolecule to amino groups in the dopamine hydrochloride is (1.7-2): 1;
the mass ratio of the solvent dimethyl sulfoxide to the dopamine hydrochloride is (6.5-15) to 1;
the number of double bonds of a multifunctional group rigid molecule is the number of double bonds of a bisacryloyl micromolecule and the number of double bonds of acrylic acid-N-succinimidyl ester =
(4-16):8:(1-4)；
Adjusting the pH value of the solution to 7.5-8.5;
the reaction temperature is 40-80 ℃, and the reaction time is 0.5-10h;
the using amount of the methyl tert-butyl ether is 5-10 times of the volume of the solution to be purified, and the purification times are 3-6 times;
the time in the vacuum dryer is 12-48h.
9. The preparation method of the hyperbranched polymer underwater adhesive as claimed in claim 1, wherein the hyperbranched polymer assembly is realized by using a solution self-assembly strategy, the hyperbranched polymer is dispersed in a poor organic solvent containing polyfunctional rigid molecules in a purification process, the hyperbranched polymer is induced to self-assemble, and finally the hyperbranched polymer assembly is precipitated and purified in methyl tert-butyl ether and repeated for a plurality of times to obtain the hyperbranched polymer assembly with the rigid hydrophobic components aggregated; the method specifically comprises the following steps: purifying the transparent solution obtained in step (3) of any one of claims 3 to 8 by using methyl tert-butyl ether as a precipitating agent, dispersing the obtained precipitate in a poor organic solvent of the multifunctional rigid molecule, and finally precipitating in the methyl tert-butyl ether for several times to obtain a hyperbranched polymer assembly; the residual poor organic solvent and precipitant were removed in a vacuum desiccator.
10. The method of preparing hyperbranched polymeric underwater adhesive of claim 9,
the using amount of the methyl tert-butyl ether is 5-10 times of the volume of the solution to be purified, and the purification times are 3-6 times;
the dosage of the poor organic solvent of the polyfunctional rigid molecule is 0.5 to 1 time of the precipitation volume;
the time in the vacuum drier is 12-48h.
11. A hyperbranched polymeric underwater adhesive based on a multifunctional rigid hydrophobic component prepared by the method of any one of claims 1 to 10.
12. Use of the hyperbranched polymer underwater adhesive based on multifunctional rigid hydrophobic components of claim 11 for adhesion under water, in air, under different humidity conditions and for adhesion of biological tissues.
13. The use of claim 12, wherein applying underwater adhesion comprises preparing adhesion samples in deionized water, PBS solution, artificial seawater, solutions of different pH values; the adhesive is applied to adhesion in air, triggered to coagulate by water spraying or soaking water, adhered in air to prepare a sample, and placed in air or soaked in deionized water, PBS solution, artificial seawater and solutions with different pH values; application to different humidity conditions comprises 0-100% RH; the biological tissue adhesive is applied to biological tissue adhesion, the adhesive is coated on the surface of the biological tissue and is triggered to coagulate by spraying water or soaking water, or the adhesive is coated on the surface of the biological tissue to be bonded after being triggered to coagulate by spraying water or soaking water.
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