CN112587715A - Preparation method of high-adhesion medical composite adhesive - Google Patents
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Abstract
The invention relates to a preparation method of a high-adhesion medical composite adhesive, and belongs to the technical field of medical adhesives. The invention takes silk fibroin fiber and catechol modified chitosan as raw materials, and betaine surfactant is added to prepare the high-adhesion medical composite adhesive, the silk fibroin has a three-dimensional network structure, good biocompatibility and a highly cross-linked spatial network structure, and the silk fibroin hydrogel has good adhesion and excellent resilience by adding the betaine surfactant. Amino exists in chitosan molecules, and a catechol group is combined on the chitosan bone dry through a chemical modification method, so that the adhesion capability and the waterproof adhesion capability of the medical adhesive can be effectively improved.
Description
Technical Field
The invention relates to a preparation method of a high-adhesion medical composite adhesive, and belongs to the technical field of medical adhesives.
Background
Medical adhesives are a very important and widely used class of novel medical materials. The advent of surgical adhesives has provided an extremely convenient means for wound healing because they exhibit several beneficial functions, such as reducing surgical suture time, reducing patient blood loss, alleviating surgical complications (e.g., infection, etc.), and ease of application. The adhesive strength of biological tissues is a very challenging task, and the adhesive material should exhibit suitable physical properties (elasticity, tensile strength, adhesive strength, etc.), biocompatibility and biodegradability when in contact with physiological fluids.
In recent years, the alpha-cyanoacrylate medical adhesive has been rapidly developed, can be decomposed into non-toxic substances in a human body and can be smoothly discharged out of the body. Therefore, the medical adhesive has the functions and advantages which are not possessed by other medical adhesives in medical science, and has the advantages of no hemolytic reaction, no heat source generation, antibacterial property and the like.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems that the existing alpha-cyanoacrylate medical adhesive has weak bonding force and can not be used for high-strength bonding, the preparation method of the high-bonding medical composite adhesive is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) respectively weighing 20-30 parts by weight of silk fibroin fiber, 10-15 parts by weight of catechol modified chitosan, 8-12 parts by weight of lithium bromide, 0.4-0.6 part by weight of dodecyl dimethyl betaine, 0.2-0.3 part by weight of tetraalkyl dimethyl betaine, 0.2-0.3 part by weight of octadecyl dimethyl betaine and 200-300 parts by weight of deionized water;
(2) adding dodecyl dimethyl betaine, tetraalkyl dimethyl betaine and octadecyl dimethyl betaine into 1/2 weight parts of deionized water, and stirring at normal temperature at a rotating speed of 140-180 r/min for 10-20 min to obtain a betaine activator solution;
(3) adding lithium bromide into the residual 1/2 parts by weight of deionized water, and stirring at the normal temperature at the rotating speed of 100-120 r/min for 10-20 min to obtain a lithium bromide solution;
(4) adding silk fibroin fibers into a lithium bromide solution, stirring at the rotating speed of 200-300 r/min for 30-40 min at the temperature of 60-70 ℃, and preserving heat to obtain a silk fibroin solution;
(5) slowly dropwise adding a betaine activator solution into the silk fibroin solution, adding catechol-modified chitosan, stirring at the rotation speed of 300-350 r/min at the temperature of 60-70 ℃ for 40-60 min, cooling at normal temperature, and standing for 12-16 h to obtain the high-adhesion medical composite adhesive.
And (4) slowly dripping the betaine activator solution at the speed of 8-10 mL/min.
The specific preparation steps of the catechol modified chitosan are as follows:
(1) respectively weighing 5-10 parts by weight of chitosan, 5-10 parts by weight of 3, 4-dihydroxyphenylacetic acid, 5-10 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 5-10 parts by weight of N-hydroxysuccinimide, 20-40 parts by weight of 10% hydrochloric acid, 50-100 parts by weight of absolute ethyl alcohol and 100-200 parts by weight of deionized water;
(2) adding chitosan and hydrochloric acid into 1/2 parts by weight of deionized water, adjusting the pH value to 5-6, and stirring at the rotating speed of 120-160 r/min for 10-20 min at normal temperature to obtain a chitosan mixed solution;
(3) quickly adding 3, 4-dihydroxy phenylacetic acid into the chitosan mixed solution, and stirring at the normal temperature at the rotating speed of 160-200 r/min for 1-3 min to obtain a reaction solution;
(4) adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and absolute ethyl alcohol into deionized water, and stirring at the normal temperature at the rotating speed of 200-300 r/min for 10-20 min to obtain a mixed solution;
(5) and slowly dropwise adding the mixed solution into the reaction solution, stirring at the rotation speed of 200-250 r/min at normal temperature for reaction for 10-12 h, then dialyzing in a hydrochloric acid solution for 3-5 days, filtering, taking a filter cake, and freeze-drying at-4-0 ℃ for 1-3 days to obtain the catechol-modified chitosan.
The pH value adjustment in the step (2) adopts a sodium hydroxide solution with the mass fraction of 1%.
And (5) slowly dripping the mixed solution at a speed of 10-20 mL/min.
And (5) the pH value of the hydrochloric acid solution in the step (5) is 5-6.
The silk fibroin fiber is prepared by the following specific steps:
(1) weighing 10-20 parts of silkworm cocoon, 5-10 parts of sodium carbonate, 5-10 parts of sodium bicarbonate and 50-100 parts of deionized water in parts by weight;
(2) adding sodium carbonate and sodium bicarbonate into deionized water, and stirring at the normal temperature at the rotating speed of 160-200 r/min for 20-30 min to obtain alkaline liquid;
(3) adding the silkworm cocoons into the alkaline solution, stirring for 2-4 h at the rotating speed of 200-240 r/min under the water bath condition of 80-90 ℃, filtering, taking filter cakes, washing for 3-5 times by using deionized water, drying for 2-4 h in an oven at the temperature of 40-50 ℃, cooling at normal temperature, and shearing to obtain the silk fibroin fibers.
And (4) the average length of the silk fibroin fibers in the step (3) is 2-4 mm.
Compared with other methods, the method has the beneficial technical effects that:
the invention takes silk fibroin fiber and catechol modified chitosan as raw materials, and betaine surfactant is added to prepare the high-adhesion medical composite adhesive, wherein the protein structure of the silk fibroin is complex and is divided into primary, secondary, tertiary and quaternary structures of the protein according to different levels. The primary structure is a primary structure, the rest is a high-grade structure, the primary structure has decisive action on the high-grade structure, the tertiary and quaternary structures are the interaction between the basic units of the secondary structure, the primary structure of the silk fibroin refers to the arrangement sequence of amino acid residues in a protein peptide chain and disulfide bonds formed among side chains of the amino acid residues, various acting forces exist among parts of one peptide chain or among several peptide chains of the silk fibroin to stabilize the spatial structure of the silk fibroin, so that hydrogel prepared by taking the silk fibroin as a raw material has a three-dimensional network structure, good biocompatibility and a highly-crosslinked spatial network structure, betaine surfactant is a typical amphoteric surfactant, the hydrophilic group of the betaine surfactant is connected with the hydrophilic group of the silk fibroin and moves, the molecular chain segment of the silk fibroin is opened, at the moment, the hydrophobic region of the silk fibroin is rapidly collapsed, and the hydrophobic group of the betaine surfactant is associated with the hydrophobic group of the activator, more new hydrophobic regions are formed, hydrogel frameworks are gradually increased to form hydrogel frameworks, and due to no ion effect, the content of beta-folding structures is not obviously increased in the formed gel frameworks, so that the silk fibroin hydrogel has good cohesiveness and excellent resilience. The chitosan is basic aminopolysaccharide which is abundantly existed in nature, the existence of amino groups enables the chitosan to have excellent antibacterial property, in addition, the chitosan also has excellent biocompatibility, biodegradability and anti-infection activity, based on the existence of amino groups in chitosan molecules, catechol groups are combined on chitosan bone stems through a chemical modification method, the bonding strength between the chitosan bone stems and tissues can be increased, and the modified chitosan with catechol structure can effectively improve the adhesion capability and the waterproof adhesion capability of the medical adhesive.
Detailed Description
Weighing 10-20 parts of silkworm cocoon, 5-10 parts of sodium carbonate, 5-10 parts of sodium bicarbonate and 50-100 parts of deionized water respectively, adding the sodium carbonate and the sodium bicarbonate into the deionized water, stirring at the normal temperature at the rotating speed of 160-200 r/min for 20-30 min to obtain alkaline liquid, adding the silkworm cocoon into the alkaline liquid, stirring at the rotating speed of 200-240 r/min for 2-4 h under the water bath condition of 80-90 ℃, filtering, taking a filter cake, washing with the deionized water for 3-5 times, drying in an oven at the temperature of 40-50 ℃ for 2-4 h, cooling at the normal temperature, and shearing to obtain silk fibroin fibers with the average length of 2-4 mm;
respectively weighing 5-10 parts by weight of chitosan, 5-10 parts by weight of 3, 4-dihydroxyphenylacetic acid, 5-10 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 5-10 parts by weight of N-hydroxysuccinimide, 20-40 parts by weight of 10% hydrochloric acid, 50-100 parts by weight of absolute ethyl alcohol and 100-200 parts by weight of deionized water, adding the chitosan and the hydrochloric acid into 1/2 parts by weight of deionized water, dropwise adding 1% by weight of sodium hydroxide solution to adjust the pH value to 5-6, stirring at the normal temperature at the rotating speed of 120-160 r/min for 10-20 min to obtain a chitosan mixed solution, rapidly adding the 3, 4-dihydroxyphenylacetic acid into the chitosan mixed solution, stirring at the normal temperature at the rotating speed of 160-200 r/min for 1-3 min to obtain a reaction solution, adding the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, adding the N-hydroxysuccinimide hydrochloride into the chitosan mixed solution, and stirring at the reaction solution, Adding N-hydroxysuccinimide and absolute ethyl alcohol into deionized water, stirring at the rotating speed of 200-300 r/min for 10-20 min at normal temperature to obtain a mixed solution, slowly dropwise adding the mixed solution into the reaction solution at the speed of 10-20 mL/min, stirring at the rotating speed of 200-250 r/min at normal temperature for 10-12 h, dialyzing in a hydrochloric acid solution with the pH of 5-6 for 3-5 days, filtering, taking a filter cake, and freeze-drying at the temperature of-4-0 ℃ for 1-3 days to obtain catechol-modified chitosan;
respectively weighing 20-30 parts by weight of silk fibroin fiber, 10-15 parts by weight of catechol-modified chitosan, 8-12 parts by weight of lithium bromide, 0.4-0.6 part by weight of dodecyl dimethyl betaine, 0.2-0.3 part by weight of tetraalkyl dimethyl betaine, 0.2-0.3 part by weight of octadecyl dimethyl betaine and 200-300 parts by weight of deionized water, adding dodecyl dimethyl betaine, tetraalkyl dimethyl betaine and octadecyl dimethyl betaine into 1/2 parts by weight of deionized water, stirring at the normal temperature of 140-180 r/min for 10-20 min to obtain a betaine activator solution, adding lithium bromide into the rest 1/2 parts by weight of deionized water, stirring at the normal temperature of 100-120 r/min for 10-20 min to obtain a lithium bromide solution, adding silk fibroin fiber into the lithium bromide solution, stirring at the temperature of 60-70 ℃ of 200-300 r/min for 30-40 min, and (3) preserving heat to obtain a silk fibroin solution, slowly dropwise adding a betaine activator solution into the silk fibroin solution at the speed of 8-10 mL/min, adding catechol-modified chitosan, stirring at the rotation speed of 300-350 r/min for 40-60 min at the temperature of 60-70 ℃, cooling at normal temperature, and standing for 12-16 h to obtain the high-adhesion medical composite adhesive.
Example 1
Weighing 10 parts of silkworm cocoon, 5 parts of sodium carbonate, 5 parts of sodium bicarbonate and 50 parts of deionized water respectively according to parts by weight, adding the sodium carbonate and the sodium bicarbonate into the deionized water, stirring at the normal temperature at the rotating speed of 160-200 r/min for 20min to obtain alkaline liquid, adding the silkworm cocoon into the alkaline liquid, stirring at the rotating speed of 200r/min for 2h under the water bath condition of 80 ℃, filtering, taking a filter cake, washing with the deionized water for 3 times, drying in a drying oven at 40 ℃ for 2h, cooling at the normal temperature, and shearing to obtain silk fibroin fibers with the average length of 2 mm;
respectively weighing 5 parts of chitosan, 5 parts of 3, 4-dihydroxyphenylacetic acid, 5 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 5 parts of N-hydroxysuccinimide, 20 parts of hydrochloric acid with the mass fraction of 10%, 50 parts of absolute ethyl alcohol and 100 parts of deionized water, adding the chitosan and the hydrochloric acid into 1/2 parts of deionized water by weight, dropwise adding a sodium hydroxide solution with the mass fraction of 1% to adjust the pH value to 5, stirring at the rotating speed of 120r/min for 10min at normal temperature to obtain a chitosan mixed solution, quickly adding the 3, 4-dihydroxyphenylacetic acid into the chitosan mixed solution, stirring at the rotating speed of 160r/min at normal temperature for 1min to obtain a reaction solution, mixing the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, and, Adding N-hydroxysuccinimide and absolute ethyl alcohol into deionized water, stirring at the rotating speed of 200r/min for 10min at normal temperature to obtain a mixed solution, slowly dropwise adding the mixed solution into the reaction solution at the speed of 10mL/min, stirring at the rotating speed of 200r/min for reaction for 10h at normal temperature, dialyzing in a hydrochloric acid solution with the pH value of 5 for 3 days, filtering, taking a filter cake, and freeze-drying at the temperature of-4 ℃ for 1 day to obtain catechol-modified chitosan;
respectively weighing 20 parts of silk fibroin fiber, 10 parts of catechol modified chitosan, 8 parts of lithium bromide, 0.4 part of dodecyl dimethyl betaine, 0.2 part of tetraalkyl dimethyl betaine, 0.2 part of octadecyl dimethyl betaine and 200 parts of deionized water according to parts by weight, adding the dodecyl dimethyl betaine, the tetraalkyl dimethyl betaine and the octadecyl dimethyl betaine into 1/2 parts of deionized water by weight, stirring at the rotating speed of 140r/min for 10min at normal temperature to obtain a betaine active agent solution, adding the lithium bromide into the rest 1/2 parts of deionized water by weight, stirring at the rotating speed of 100r/min for 10min at normal temperature to obtain a lithium bromide solution, adding the silk fibroin fiber into the lithium bromide solution, stirring at the rotating speed of 200r/min at the temperature of 60 ℃ for 30min, preserving heat to obtain a silk fibroin solution, slowly adding the betaine active agent solution into the silk fibroin solution at the speed of 8mL/min, adding catechol modified chitosan, stirring at the rotation speed of 300r/min for 40min at the temperature of 60 ℃, cooling at normal temperature, and standing for 12h to obtain the high-adhesion medical composite adhesive.
Example 2
Weighing 15 parts of silkworm cocoon, 7.5 parts of sodium carbonate, 7.5 parts of sodium bicarbonate and 75 parts of deionized water respectively according to parts by weight, adding the sodium carbonate and the sodium bicarbonate into the deionized water, stirring for 25min at the normal temperature at the rotating speed of 180r/min to obtain alkaline liquid, adding the silkworm cocoon into the alkaline liquid, stirring for 3h at the rotating speed of 220r/min under the condition of water bath at the temperature of 85 ℃, filtering, taking a filter cake, washing for 4 times with the deionized water, drying for 3h in a drying oven at the temperature of 45 ℃, cooling at the normal temperature, and shearing to obtain silk fibroin fibers with the average length of 3 mm;
respectively weighing 7.5 parts of chitosan, 7.5 parts of 3, 4-dihydroxyphenylacetic acid, 7.5 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 7.5 parts of N-hydroxysuccinimide, 30 parts of hydrochloric acid with the mass fraction of 10%, 75 parts of absolute ethyl alcohol and 150 parts of deionized water, adding the chitosan and the hydrochloric acid into 1/2 parts of deionized water by weight, dropwise adding a sodium hydroxide solution with the mass fraction of 1% to adjust the pH value to 5.5, stirring at the normal temperature at the rotating speed of 140r/min for 15min to obtain a chitosan mixed solution, quickly adding the 3, 4-dihydroxyphenylacetic acid into the chitosan mixed solution, stirring at the normal temperature at the rotating speed of 180r/min for 2min to obtain a reaction solution, adding the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, adding the N-hydroxysuccinimide hydrochloride into the chitosan mixed solution, stirring at the normal temperature at the rotating speed of 180r/, Adding N-hydroxysuccinimide and absolute ethyl alcohol into deionized water, stirring at the rotating speed of 250r/min for 15min at normal temperature to obtain a mixed solution, slowly dropwise adding the mixed solution into the reaction solution at the speed of 15mL/min, stirring at the rotating speed of 225r/min at normal temperature for reaction for 11h, dialyzing in a hydrochloric acid solution with the pH value of 5.5 for 4 days, filtering, taking a filter cake, and freeze-drying at the temperature of-2 ℃ for 2 days to obtain catechol-modified chitosan;
respectively weighing 25 parts by weight of silk fibroin fiber, 12.5 parts by weight of catechol-modified chitosan, 10 parts by weight of lithium bromide, 0.5 part by weight of dodecyl dimethyl betaine, 0.25 part by weight of tetraalkyl dimethyl betaine, 0.25 part by weight of octadecyl dimethyl betaine and 250 parts by weight of deionized water, adding dodecyl dimethyl betaine, tetraalkyl dimethyl betaine and octadecyl dimethyl betaine into 1/2 parts by weight of deionized water, stirring at the rotating speed of 160r/min for 15min at normal temperature to obtain a betaine active agent solution, adding lithium bromide into the rest 1/2 parts by weight of deionized water, stirring at the rotating speed of 110r/min for 15min at normal temperature to obtain a lithium bromide solution, adding silk fibroin fiber into the lithium bromide solution, stirring at the rotating speed of 250r/min for 35min at the temperature of 65 ℃, preserving heat to obtain a silk fibroin solution, slowly dripping the betaine active agent solution into the silk fibroin solution at the speed of 9mL/min, adding catechol modified chitosan, stirring at the rotation speed of 325r/min for 50min at the temperature of 65 ℃, cooling at normal temperature, and standing for 14h to obtain the high-adhesion medical composite adhesive.
Example 3
Weighing 20 parts of silkworm cocoon, 10 parts of sodium carbonate, 10 parts of sodium bicarbonate and 100 parts of deionized water respectively according to parts by weight, adding the sodium carbonate and the sodium bicarbonate into the deionized water, stirring for 30min at the rotating speed of 200r/min at normal temperature to obtain alkaline liquid, adding the silkworm cocoon into the alkaline liquid, stirring for 4h at the rotating speed of 240r/min under the condition of 90 ℃ water bath, filtering, taking a filter cake, washing for 5 times with the deionized water, drying for 4h in a 50 ℃ drying oven, cooling at normal temperature, and shearing to obtain silk fibroin fiber with the average length of 4 mm;
respectively weighing 10 parts of chitosan, 10 parts of 3, 4-dihydroxyphenylacetic acid, 10 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 10 parts of N-hydroxysuccinimide, 40 parts of hydrochloric acid with the mass fraction of 10%, 100 parts of absolute ethyl alcohol and 200 parts of deionized water, adding the chitosan and the hydrochloric acid into 1/2 parts of deionized water by weight, dropwise adding a sodium hydroxide solution with the mass fraction of 1% to adjust the pH value to 6, stirring at the normal temperature for 20min at the rotating speed of 160r/min to obtain a chitosan mixed solution, quickly adding the 3, 4-dihydroxyphenylacetic acid into the chitosan mixed solution, stirring at the normal temperature at the rotating speed of 200r/min for 3min to obtain a reaction solution, mixing the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, and, Adding N-hydroxysuccinimide and absolute ethyl alcohol into deionized water, stirring at the rotating speed of 300r/min for 20min at normal temperature to obtain a mixed solution, slowly dropwise adding the mixed solution into the reaction solution at the speed of 20mL/min, stirring at the rotating speed of 250r/min at normal temperature for reaction for 12h, then dialyzing in a hydrochloric acid solution with the pH value of 6 for 5 days, filtering, taking a filter cake, and freeze-drying at the temperature of 0 ℃ for 3 days to obtain catechol-modified chitosan;
then respectively weighing 30 parts of silk fibroin fiber, 15 parts of catechol modified chitosan, 12 parts of lithium bromide, 0.6 part of dodecyl dimethyl betaine, 0.3 part of tetraalkyl dimethyl betaine, 0.3 part of octadecyl dimethyl betaine and 300 parts of deionized water according to parts by weight, adding the dodecyl dimethyl betaine, the tetraalkyl dimethyl betaine and the octadecyl dimethyl betaine into 1/2 parts of deionized water by weight, stirring at 180r/min for 20min at normal temperature to obtain a betaine active agent solution, adding the lithium bromide into the rest 1/2 parts of deionized water by weight, stirring at 120r/min at normal temperature for 20min to obtain a lithium bromide solution, adding the silk fibroin fiber into the lithium bromide solution, stirring at 300r/min for 40min at 70 ℃, preserving the temperature to obtain a silk fibroin solution, slowly adding the betaine active agent solution into the silk fibroin solution at a rate of 10mL/min, adding catechol modified chitosan, stirring at the rotation speed of 350r/min for 60min at the temperature of 70 ℃, cooling at normal temperature, and standing for 16h to obtain the high-adhesion medical composite adhesive.
Claims (8)
1. A preparation method of a high-adhesion medical composite adhesive is characterized by comprising the following specific preparation steps:
(1) respectively weighing 20-30 parts by weight of silk fibroin fiber, 10-15 parts by weight of catechol modified chitosan, 8-12 parts by weight of lithium bromide, 0.4-0.6 part by weight of dodecyl dimethyl betaine, 0.2-0.3 part by weight of tetraalkyl dimethyl betaine, 0.2-0.3 part by weight of octadecyl dimethyl betaine and 200-300 parts by weight of deionized water;
(2) adding dodecyl dimethyl betaine, tetraalkyl dimethyl betaine and octadecyl dimethyl betaine into 1/2 weight parts of deionized water, and stirring at normal temperature at a rotating speed of 140-180 r/min for 10-20 min to obtain a betaine activator solution;
(2) adding lithium bromide into the residual 1/2 parts by weight of deionized water, and stirring at the normal temperature at the rotating speed of 100-120 r/min for 10-20 min to obtain a lithium bromide solution;
(3) adding silk fibroin fibers into a lithium bromide solution, stirring at the rotating speed of 200-300 r/min for 30-40 min at the temperature of 60-70 ℃, and preserving heat to obtain a silk fibroin solution;
(4) slowly dropwise adding a betaine activator solution into the silk fibroin solution, adding catechol-modified chitosan, stirring at the rotation speed of 300-350 r/min at the temperature of 60-70 ℃ for 40-60 min, cooling at normal temperature, and standing for 12-16 h to obtain the high-adhesion medical composite adhesive.
2. The preparation method of the high-adhesion medical composite adhesive as claimed in claim 1, wherein the slow dropping rate of the betaine activator solution in the step (4) is 8-10 mL/min.
3. The preparation method of the high-adhesion medical composite adhesive according to claim 1, wherein the catechol-modified chitosan prepared in the step (1) is prepared by the following steps:
(1) respectively weighing 5-10 parts by weight of chitosan, 5-10 parts by weight of 3, 4-dihydroxyphenylacetic acid, 5-10 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 5-10 parts by weight of N-hydroxysuccinimide, 20-40 parts by weight of 10% hydrochloric acid, 50-100 parts by weight of absolute ethyl alcohol and 100-200 parts by weight of deionized water;
(2) adding chitosan and hydrochloric acid into 1/2 parts by weight of deionized water, adjusting the pH value to 5-6, and stirring at the rotating speed of 120-160 r/min for 10-20 min at normal temperature to obtain a chitosan mixed solution;
(3) quickly adding 3, 4-dihydroxy phenylacetic acid into the chitosan mixed solution, and stirring at the normal temperature at the rotating speed of 160-200 r/min for 1-3 min to obtain a reaction solution;
(4) adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and absolute ethyl alcohol into deionized water, and stirring at the normal temperature at the rotating speed of 200-300 r/min for 10-20 min to obtain a mixed solution;
(5) and slowly dropwise adding the mixed solution into the reaction solution, stirring at the rotation speed of 200-250 r/min at normal temperature for reaction for 10-12 h, then dialyzing in a hydrochloric acid solution for 3-5 days, filtering, taking a filter cake, and freeze-drying at-4-0 ℃ for 1-3 days to obtain the catechol-modified chitosan.
4. The method for preparing the high-adhesion medical composite adhesive according to claim 3, wherein the pH adjustment in the step (2) is performed by using a sodium hydroxide solution with a mass fraction of 1%.
5. The preparation method of the high-adhesion medical composite adhesive according to claim 3, wherein the slow dropping rate of the mixed solution in the step (5) is 10-20 mL/min.
6. The preparation method of the high-adhesion medical composite adhesive according to claim 3, wherein the pH value of the hydrochloric acid solution in the step (5) is 5-6.
7. The preparation method of the high-adhesion medical composite adhesive according to claim 1, wherein the silk fibroin fibers prepared in the step (1) are prepared by the following specific steps:
(1) weighing 10-20 parts of silkworm cocoon, 5-10 parts of sodium carbonate, 5-10 parts of sodium bicarbonate and 50-100 parts of deionized water in parts by weight;
(2) adding sodium carbonate and sodium bicarbonate into deionized water, and stirring at the normal temperature at the rotating speed of 160-200 r/min for 20-30 min to obtain alkaline liquid;
(3) adding the silkworm cocoons into the alkaline solution, stirring for 2-4 h at the rotating speed of 200-240 r/min under the water bath condition of 80-90 ℃, filtering, taking filter cakes, washing for 3-5 times by using deionized water, drying for 2-4 h in an oven at the temperature of 40-50 ℃, cooling at normal temperature, and shearing to obtain the silk fibroin fibers.
8. The preparation method of the high-adhesion medical composite adhesive according to claim 7, wherein the average length of the silk fibroin fibers in the step (3) is 2-4 mm.
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