CN104262634B - A kind of preparation method of organosilicon collagen polypeptide anti-biotic material - Google Patents
A kind of preparation method of organosilicon collagen polypeptide anti-biotic material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of organosilicon collagen polypeptide anti-biotic material, synthesis including (1) epoxy polysiloxane quaternary ammonium salt, the hydrolysis of (2) collagen polypeptide and three steps of synthesis of (3) organosilicon collagen polypeptide anti-biotic material.The present invention is reacted using the high reaction activity of epoxy in epoxy polysiloxane quaternary ammonium salt with collagen polypeptide hydrolyzate, ring-opening reaction i.e. by epoxy guides on siloxane chain the collagen polypeptide small molecule after hydrolysis, organosilicon collagen polypeptide material is prepared, preparation process is simple；The organosilicon collagen polypeptide material of synthesis is respectively provided with good bacteriostasis antibiosis to gram-positive bacteria and Gram-negative bacteria, especially has good anti-microbial property to staphylococcus aureus.
Description
Technical Field
The invention belongs to the field of natural polymers, relates to a preparation method of a collagen polypeptide material, and particularly relates to a preparation method of an organic silicon-collagen polypeptide antibacterial material.
Background
Collagen polypeptide (collagen) is the protein biological macromolecule with the largest content in mammals, and plays a plurality of roles of supporting, protecting, connecting and the like in vivo. The collagen polypeptide has the characteristics of excellent biodegradability, low antigenicity, super-biocompatibility and the like, has strong hydrophilicity, high tensile strength, no toxicity and good safety, is considered to be one of better natural biological materials, and is widely applied to the fields of medicines, chemical industry, foods, cosmetics, bioengineering and the like. However, natural collagen polypeptide molecules have some defects, such as high molecular weight, poor absorption, poor mechanical properties, easy deterioration, etc., and the defects need to be overcome by a chemical improvement method. The hydrolyzed low molecular weight collagen polypeptide has the same chemical composition, so that it has most of the excellent physical and chemical performance, including colloid protection, surface activity, water maintaining performance, adhesion, emulsification, foaming, etc. maintained and is easy to be absorbed by human body, skin, etc. owing to the lowered molecular weight and raised solubility. Therefore, the collagen polypeptide is firstly hydrolyzed, so that the active groups in the molecule can be more effectively utilized and expanded; secondly, the hydrolysate can be more effectively used for preparing beauty cosmetics, biomedical materials, health products, food coating and packaging materials, leather retanning fillers, finishing agents and the like after being chemically grafted and modified by a chemical method.
At present, a plurality of researchers perform modification exploration on collagen polypeptides in different modes so as to overcome the defects of the collagen polypeptides and improve the applicability of the collagen polypeptides. Glutaraldehyde is selected as a modifying reagent to modify the collagen, and after aldehyde groups of the glutaraldehyde and amino groups of the collagen are subjected to specific crosslinking, the aldehyde groups and the blocked amino groups of the collagen can be increased, and the molecular mass of the protein is changed, so that certain functional characteristics of the protein are changed, the protein has low toxicity, and the collagen has the advantages of high activity, quick reaction, high binding capacity, good crosslinking performance, stable product and the like when reacting with the protein. Thus, the collagen can be modified to form a new substance to expand the application range (glutaraldehyde modification research for extracting collagen from waste chrome leather scrap in Caojiao [ J ] Chinese leather 2005,34 (5): 21-26). In addition, chinese patent document CN103319729A discloses a method for modifying functional gelatin; the gelatin modified by the 3, 4-dihydroxybenzoyl chloride modifier has the isoelectric point reduced to pH 1.7-2.1, and is formed into a precipitate in artificial gastric juice without disintegration, and the degree of hydrolysis side reaction is controllable by quantitative analysis of polyacrylamide gel electrophoresis. The hydrolysis degree of the gelatin is controllable, and the hydrolyzed small molecular polypeptide is easy to be absorbed by human body and has health care function.
Chinese patent document CN1640913A discloses a preparation method of cross-linked chitosan-quaternized hydrolyzed collagen, relating to the preparation of antibacterial biological materials; silkworm chrysalis chitosan and hydrolyzed collagen are used as raw materials, a cross-linking agent is added for cross-linking reaction to prepare a solution or gel product, and then various functional factors are added, so that the prepared biological dressing has the characteristics of good antibacterial property, good air permeability and the like, and can be widely used for wound repair, sterilization and the like. Methacryloyloxyethyl-tetradecyl-dimethyl ammonium bromide is grafted to the surface of collagen polypeptide through double bonds of the methacryloyloxyethyl-tetradecyl-dimethyl ammonium bromide, antibacterial groups are grafted to the surface of a natural polymer, the polymer antibacterial material is synthesized, and a new way is opened up for expanding the application range of collagen. However, the sterilization mechanism of the polymeric quaternary ammonium salt antibacterial material is not yet clear (Rawangian. Synthesis, characterization and biological activity of quaternary ammonium salt type collagen derivative [ J ] proceedings of Industrial university of Henan, 2008,29 (2): 55-58)
Chinese patent document CN101831723A discloses a preparation method of trivalent cerium modified gelatin bacteriostatic fiber. The trivalent cerium solution and the gelatin solution are blended, and the gelatin fiber prepared by solution spinning has the characteristics of antibiosis, anticoagulation, water resistance and the like, so that the gelatin fiber has wide application prospects in the fields of medicine, textile and the like.
Although many documents research the modification of gelatin in order to optimize properties and expand application range, the modified gelatin still has many problems, such as poor antibacterial performance, easy mildew, unstable product storage, and aging resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an organosilicon-collagen polypeptide antibacterial material.
The technical scheme of the invention is as follows:
a preparation method of an organic silicon-collagen polypeptide antibacterial material comprises the following steps:
(1) synthesis of epoxy polysiloxane quaternary ammonium salt
Dissolving tertiary amino silicone oil in absolute ethyl alcohol, slowly dripping an absolute ethyl alcohol solution of epoxy chloropropane at 40-60 ℃, and keeping the temperature to react for 6-8 h; after the reaction is finished, cooling to room temperature, rotationally evaporating the absolute ethyl alcohol solvent, eluting for 6-8 times by using absolute ethyl ether, and drying in vacuum for 20-30 hours to obtain epoxy polysiloxane quaternary ammonium salt;
(2) hydrolysis of collagen polypeptides
Preparing a collagen polypeptide aqueous solution with the concentration of 2-12 wt%, hydrolyzing under an alkaline condition, adjusting the pH value of the solution to 7.0-13, slowly heating to 30-65 ℃, and hydrolyzing for 5-9 h to obtain a collagen polypeptide hydrolysate;
(3) synthesis of organosilicon-collagen polypeptide antibacterial material
According to the molar ratio of (1-2) to 1 of epoxy polysiloxane quaternary ammonium salt to primary amino group in the collagen polypeptide hydrolysate, dripping the epoxy polysiloxane quaternary ammonium salt into the collagen polypeptide hydrolysate, and reacting for 2-8 hours under the condition of stirring at the temperature of 30-65 ℃; adjusting the pH value of the solution after reaction to be neutral; and (3) distilling under reduced pressure to remove 50-80% of water, and freeze-drying at-60 to-40 ℃ for 20-50 h to obtain the organic silicon-collagen polypeptide antibacterial material.
According to the invention, the molar ratio of the tertiary amino silicone oil to the epichlorohydrin in the step (1) is preferably 1 (1.2-1.5); the reaction temperature is 45-50 ℃.
According to the invention, the silicone oil with different tertiary amino group contents is used in the step (1) to obtain epoxy polysiloxane quaternary ammonium salts with different quaternary ammonium group contents; preferably, the amine value of the tertiary amino silicone oil is 2.500mmol/g to 4.500 mmol/g. The absolute ethyl alcohol is used as a reaction solvent, and the tertiary amino silicone oil and the epoxy chloropropane are dissolved; preferably, the molecular weight of the prepared epoxy polysiloxane quaternary ammonium salt is preferably 3000-8000.
According to the invention, preferably, the pH value of the solution is adjusted to 9.0-11 in the step (2), and the hydrolysis temperature is 40-60 ℃.
According to the invention, the reaction temperature in the step (3) is preferably 40-60 ℃;
preferably, after freeze drying, refluxing and extracting for 65-80h by using acetone solution, and removing unreacted epoxy polysiloxane quaternary ammonium salt.
The invention adopts epoxy polysiloxane quaternary ammonium salt to react with collagen polypeptide hydrolysate to prepare the organosilicon-collagen polypeptide material with antibacterial and antibacterial properties, and has wide application prospect in the industries of food, medical, cosmetics and the like. Meanwhile, due to the similarity of the structure, the polypeptide has good compatibility with the collagen, can be used for preparing leather auxiliaries and soft finishing agent materials, and is a low-toxicity, green and environment-friendly bacteriostatic and antibacterial material.
The reaction route of the invention is as follows:
wherein,
wherein
R2Is selected from alkanes of C1-C18, preferably alkanes of C2-C5; r3Is selected from alkanes of C1-C18, preferably alkanes of C2-C4; r4Is selected from alkanes of C1-C18, preferably alkanes of C2-C4.
The tertiary amino silicone oil is a conventional raw material, can be purchased in the market, and can also be prepared according to the prior art;
preferably, the preparation method comprises the following steps:
(i) adding gamma-chloropropylmethyldimethoxysilane and diethylamine into a high-pressure reaction kettle under the atmosphere of high-purity nitrogen according to the mol ratio of 1 (4-6), reacting for 18-25h at the temperature of 105-; the filtrate was subjected to atmospheric distillation to remove excess diethylamine; then carrying out reduced pressure distillation, and collecting stable fractions to obtain colorless or light yellow transparent liquid N, N-diethyl-aminopropyl methyl dimethoxy silane;
(ii) hydrolyzing N, N-diethyl-aminopropylmethyldimethoxysilane in NaOH alkaline condition, and reacting the hydrolysate with octamethylcyclotetrasiloxane (D)4) Carrying out equilibrium polymerization for 4-8h under the conditions that KOH is used as a catalyst and hexamethyldisiloxane (MM) is used as an end-capping agent, neutralizing KOH with glacial acetic acid, filtering, and distilling under reduced pressure to remove small-molecular low-boiling-point substances to obtain light yellow tertiary amine silicon oil;
the molar ratio of the hydrolysate to the octamethylcyclotetrasiloxane is 1: 1.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, high reactivity of epoxy in epoxy polysiloxane quaternary ammonium salt is utilized to react with collagen polypeptide hydrolysate, namely hydrolyzed collagen polypeptide micromolecules are introduced to a siloxane chain through ring-opening reaction of the epoxy, so that the organosilicon-collagen polypeptide material is prepared, and the preparation process is simple.
2. After the collagen polypeptide is hydrolyzed, the primary amino group content is increased, so that the active group can be more effectively utilized, the conversion rate is high, the reaction condition is mild, the energy consumption is low, and the process is easy to control.
3. The collagen polypeptide material prepared by the invention contains the organic silicon group, so that the collagen polypeptide material has stable property and strong anti-aging characteristic.
4. The organosilicon-collagen polypeptide material synthesized by the invention has good bacteriostatic and antibacterial properties on gram-positive bacteria and gram-negative bacteria, and particularly has good antibacterial property on staphylococcus aureus.
Drawings
FIG. 1 is a graph showing the effect of epoxy polysiloxane quaternary ammonium salt synthesized in step (1) of example 3 on the antibacterial performance of Staphylococcus aureus.
Fig. 2 is a diagram showing the test effect of the antibacterial property of the leather against staphylococcus aureus after the organosilicon-collagen polypeptide antibacterial material synthesized in example 3 of the invention is applied to the leather. Wherein, a represents the front surface of the original leather without the organosilicon-collagen polypeptide antibacterial material, b represents the back surface of the original leather without the organosilicon-collagen polypeptide antibacterial material, and c represents the front surface and the back surface of the leather after the organosilicon-collagen polypeptide antibacterial material is added.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Most of the raw materials used in the invention are conventional raw materials and are commercially available products.
Wherein, tertiary amino silicone oil: the preparation method comprises the following steps:
(i) gamma-chloropropylmethyldimethoxysilane and diethylamine are used as raw materials (the molar ratio is 1: 4), added into a high-pressure reaction kettle under the atmosphere of high-purity nitrogen, reacted for 20 hours at the temperature of 110 ℃ and the pressure of 0.5MPa, stopped heating, cooled to room temperature, and filtered to remove solids (diethylamine hydrochloride); the filtrate was yellow and transparent, and atmospheric distillation was carried out to remove excess diethylamine; then carrying out reduced pressure distillation, and collecting stable fractions to obtain colorless or light yellow transparent liquid N, N-diethyl-aminopropyl methyl dimethoxy silane (the purity is 97.4%);
(ii) hydrolyzing N, N-diethyl-aminopropylmethyldimethoxysilane in NaOH alkaline condition, and reacting the hydrolysate with octamethylcyclotetrasiloxane (D)4) (molar ratio of 1: 1) carrying out equilibrium polymerization for 6h under the conditions of using KOH as a catalyst and hexamethyldisiloxane (MM) as an end-capping agent, neutralizing the KOH by glacial acetic acid, filtering, and distilling under reduced pressure to remove small-molecular low-boiling-point substances to obtain light yellow tertiary amine silicon oil.
Collagen polypeptide: chemical agents of the national drug group, ltd.
Example 1
A preparation method of an organic silicon-collagen polypeptide antibacterial material comprises the following steps:
(1) synthesis of epoxy polysiloxane quaternary ammonium salt
Dissolving 8g of tertiary amino silicone oil with the amine value of 3.562mmol/g and the molecular weight of 3580 in 16mL of absolute ethyl alcohol, slowly dropwise adding an absolute ethyl alcohol solution of epoxy chloropropane (3.165g of epoxy chloropropane and 8mL of absolute ethyl alcohol) at 40 ℃, and keeping the temperature to react for 8 hours; after the reaction is finished, cooling to room temperature, rotationally evaporating the absolute ethyl alcohol solvent, eluting for 6 times by using absolute ethyl ether, and drying for 20 hours in vacuum to obtain epoxy polysiloxane quaternary ammonium salt with the molecular weight of 4759;
(2) hydrolysis of collagen polypeptides
Preparing a collagen polypeptide aqueous solution with the concentration of 6 wt%, and heating to 45 ℃ under the alkaline condition of pH 10 to hydrolyze for 6h to obtain collagen polypeptide hydrolysate;
(3) synthesis of organosilicon-collagen polypeptide antibacterial material
Dropping 1.94g of epoxy polysiloxane quaternary ammonium salt into 4g of collagen polypeptide hydrolysate according to the molar ratio of the epoxy polysiloxane quaternary ammonium salt to primary amino groups in the collagen polypeptide hydrolysate of 1:1, and reacting for 6 hours under the condition of stirring and keeping the temperature at 50 ℃; adjusting the pH value of the solution after reaction to be neutral; distilling under reduced pressure to remove 80% of water, freeze-drying at-49 deg.C for 24 hr, freeze-drying, and Soxhlet extracting with acetone solution for 72 hr to obtain organosilicon-collagen polypeptide antibacterial material.
Example 2
A preparation method of an organic silicon-collagen polypeptide antibacterial material comprises the following steps:
(1) synthesis of epoxy polysiloxane quaternary ammonium salt
Dissolving 6g of tertiary amino silicone oil with the amine value of 3.562mmol/g and the molecular weight of 3580 in 12mL of absolute ethyl alcohol, slowly dropwise adding an absolute ethyl alcohol solution of epoxy chloropropane (2.372g of epoxy chloropropane and 5mL of absolute ethyl alcohol) at 50 ℃, and keeping the temperature to react for 7 hours; after the reaction is finished, cooling to room temperature, rotationally evaporating the absolute ethyl alcohol solvent, eluting for 6 times by using absolute ethyl ether, and drying for 25 hours in vacuum to obtain epoxy polysiloxane quaternary ammonium salt with the molecular weight of 4759;
(2) hydrolysis of collagen polypeptides
Preparing a collagen polypeptide aqueous solution with the concentration of 8 wt%, and heating to 45 ℃ under the alkaline condition of pH 12 for hydrolysis for 8h to obtain collagen polypeptide hydrolysate;
(3) synthesis of organosilicon-collagen polypeptide antibacterial material
Dropping 3.01g of epoxy polysiloxane quaternary ammonium salt into 6g of collagen polypeptide hydrolysate according to the molar ratio of the epoxy polysiloxane quaternary ammonium salt to primary amino groups in the collagen polypeptide hydrolysate of 1.2:1, and reacting for 6 hours under the condition of stirring and keeping the temperature at 50 ℃; adjusting the pH value of the solution after reaction to be neutral; distilling under reduced pressure to remove 70% of water, freeze-drying at-49 deg.C for 24 hr, freeze-drying, and Soxhlet extracting with acetone solution for 65 hr to obtain organosilicon-collagen polypeptide antibacterial material.
Example 3
A preparation method of an organic silicon-collagen polypeptide antibacterial material comprises the following steps:
(1) synthesis of epoxy polysiloxane quaternary ammonium salt
Dissolving 6g of tertiary amino silicone oil with the amine value of 3.152mmol/g and the molecular weight of 2493 in 12mL of absolute ethyl alcohol, slowly dropwise adding an absolute ethyl alcohol solution of epoxy chloropropane (2.010g of epoxy chloropropane and 6mL of absolute ethyl alcohol) at 60 ℃, and keeping the temperature to react for 6 hours; after the reaction is finished, cooling to room temperature, rotationally evaporating the absolute ethyl alcohol solvent, eluting with absolute ethyl ether for 6 times, and drying in vacuum for 28 hours to obtain epoxy polysiloxane quaternary ammonium salt with the molecular weight of 3220;
(2) hydrolysis of collagen polypeptides
Preparing a collagen polypeptide aqueous solution with the concentration of 8 wt%, and heating to 45 ℃ under the alkaline condition of pH 10 to hydrolyze for 6h to obtain collagen polypeptide hydrolysate;
(3) synthesis of organosilicon-collagen polypeptide antibacterial material
Dripping 2.22g of epoxy polysiloxane quaternary ammonium salt into 4g of collagen polypeptide hydrolysate according to the molar ratio of the epoxy polysiloxane quaternary ammonium salt to primary amino groups in the collagen polypeptide hydrolysate of 1.5:1, and reacting for 8 hours under the condition of stirring and keeping the temperature at 50 ℃; adjusting the pH value of the solution after reaction to be neutral; distilling under reduced pressure to remove 60% of water, freeze-drying at-49 deg.C for 24 hr, freeze-drying, and Soxhlet extracting with acetone solution for 72 hr to obtain organosilicon-collagen polypeptide antibacterial material.
Example 4
A preparation method of an organic silicon-collagen polypeptide antibacterial material comprises the following steps:
(1) synthesis of epoxy polysiloxane quaternary ammonium salt
Dissolving 5g of tertiary amino silicone oil with the amine value of 3.152mmol/g and the molecular weight of 2493 in 10mL of absolute ethyl alcohol, slowly dropwise adding an absolute ethyl alcohol solution of epoxy chloropropane (1.749g of epoxy chloropropane and 4mL of absolute ethyl alcohol) at 60 ℃, and keeping the temperature to react for 6 hours; after the reaction is finished, cooling to room temperature, rotationally evaporating the absolute ethyl alcohol solvent, eluting with absolute ethyl ether for 6 times, and drying in vacuum for 28 hours to obtain epoxy polysiloxane quaternary ammonium salt with the molecular weight of 3220;
(2) hydrolysis of collagen polypeptides
Preparing a collagen polypeptide aqueous solution with the concentration of 10 wt%, heating to 45 ℃ under the alkaline condition of pH 12, and hydrolyzing for 8h to obtain collagen polypeptide hydrolysate;
(3) synthesis of organosilicon-collagen polypeptide antibacterial material
Dripping 5.57g of epoxy polysiloxane quaternary ammonium salt into 6g of collagen polypeptide hydrolysate according to the molar ratio of the epoxy polysiloxane quaternary ammonium salt to primary amino groups in the collagen polypeptide hydrolysate of 1.5:1, and reacting for 6 hours under the condition of stirring at the temperature of 50 ℃; adjusting the pH value of the solution after reaction to be neutral; distilling under reduced pressure to remove 60% of water, freeze-drying at-55 deg.C for 36h, freeze-drying, and Soxhlet extracting with acetone solution for 72h to obtain organosilicon-collagen polypeptide antibacterial material.
Example 5
A preparation method of an organic silicon-collagen polypeptide antibacterial material comprises the following steps:
(1) synthesis of epoxy polysiloxane quaternary ammonium salt
Dissolving 6g of tertiary amino silicone oil with an amine value of 3.449mmol/g and a molecular weight of 4165 in 12mL of absolute ethanol, slowly dropwise adding an absolute ethanol solution of epichlorohydrin (2.297g of epichlorohydrin and 6mL of absolute ethanol) at 50 ℃, and keeping the temperature for reaction for 7 hours; after the reaction is finished, cooling to room temperature, rotationally evaporating the absolute ethyl alcohol solvent, eluting with absolute ethyl ether for 6 times, and drying in vacuum for 25 hours to obtain epoxy polysiloxane quaternary ammonium salt with molecular weight of 7683;
(2) hydrolysis of collagen polypeptides
Preparing a collagen polypeptide aqueous solution with the concentration of 10 wt%, heating to 45 ℃ under the alkaline condition of pH 12, and hydrolyzing for 8h to obtain collagen polypeptide hydrolysate;
(3) synthesis of organosilicon-collagen polypeptide antibacterial material
Dripping 4.83g of epoxy polysiloxane quaternary ammonium salt into 5g of collagen polypeptide hydrolysate according to the molar ratio of the epoxy polysiloxane quaternary ammonium salt to primary amino groups in the collagen polypeptide hydrolysate of 1.5:1, and reacting for 8 hours under the condition of stirring and keeping the temperature at 50 ℃; adjusting the pH value of the solution after reaction to be neutral; distilling under reduced pressure to remove 50% of water, freeze-drying at-40 deg.C for 48h, freeze-drying, and Soxhlet extracting with acetone solution for 75h to obtain organosilicon-collagen polypeptide antibacterial material.
Experimental example 1
The epoxy polysiloxane quaternary ammonium salt prepared in step (1) of example 3 was tested for antibacterial properties against staphylococcus aureus by the following steps:
the filter paper was cut into circular pieces of paper having a diameter of 1.2cm, immersed in 0.5mg/mL solution of epoxy silicone quaternary ammonium salt for 30s, taken out and pressed once with a glass plate. Adding 20mL of culture medium into a culture dish, coating 15 mu L of staphylococcus aureus liquid after solidification, then placing a filter paper sheet, culturing for 24 hours at 37 ℃ in an incubator, and carrying out three experiments in parallel to observe that an obvious circle of non-growing bacteria can be formed on the culture medium. The size of the inhibition zone can indicate the strength of the antibacterial property.
The test result is shown in fig. 1, and as can be seen from fig. 1, a clear and transparent inhibition zone is formed around the circular filter paper sheet soaked by the epoxy polysiloxane quaternary ammonium salt, which indicates that no bacteria grow around the circular filter paper, and the bacteria grow in other areas, which indicates that the circular filter paper sheet has a good inhibition effect on staphylococcus aureus.
Experimental example 2
The organosilicon-collagen polypeptide antibacterial material product prepared in the embodiment 3 is tested for the antibacterial performance to staphylococcus aureus, and the steps are as follows:
the raw leather sheet and the leather sheet added with the organosilicon-collagen polypeptide antibacterial material are cut into circular sheets with the diameter of 1.2cm for standby. Then 20mL of culture medium is added into the culture dish, 15 muL of staphylococcus aureus liquid is coated after solidification, then a cut leather wafer is placed on the culture dish, the culture is carried out for 24 hours at 37 ℃ in an incubator, and an obvious circle of non-growing bacteria is observed to be formed on the culture medium in parallel with three experiments. The size of the inhibition zone can indicate the strength of the antibacterial property.
The test results are shown in fig. 2, wherein a represents the front surface of the leather without the organosilicon-collagen polypeptide antibacterial material, b represents the back surface of the leather without the organosilicon-collagen polypeptide antibacterial material, and c represents the front surface and the back surface of the leather after the organosilicon-collagen polypeptide antibacterial material is added. As can be seen from figure 2, the original leather has no bacteriostatic effect on Staphylococcus aureus, and a clear bacteriostatic circle is formed around the leather wafer after the organosilicon-collagen polypeptide antibacterial material is added, which shows that the leather wafer has antibacterial effect, and compared with figure 1, the leather wafer has good antibacterial effect.
Claims (3)
1. A preparation method of an organic silicon-collagen polypeptide antibacterial material comprises the following steps:
(1) synthesis of epoxy polysiloxane quaternary ammonium salt
Dissolving tertiary amino silicone oil in absolute ethyl alcohol, slowly dropwise adding an absolute ethyl alcohol solution of epoxy chloropropane at 45-50 ℃, and keeping the temperature to react for 6-8 h; after the reaction is finished, cooling to room temperature, rotationally evaporating the absolute ethyl alcohol solvent, eluting for 6-8 times by using absolute ethyl ether, and drying in vacuum for 20-30 hours to obtain epoxy polysiloxane quaternary ammonium salt;
the molar ratio of the tertiary amino silicone oil to the epoxy chloropropane is 1 (1.2-1.5);
the amine value of the tertiary amino silicone oil is 2.500 mmol/g-4.500 mmol/g;
the molecular weight of the prepared epoxy polysiloxane quaternary ammonium salt is 3000-8000;
(2) hydrolysis of collagen polypeptides
Preparing a collagen polypeptide aqueous solution with the concentration of 2-12 wt%, hydrolyzing under an alkaline condition, adjusting the pH value of the solution to 9.0-11, slowly heating to 40-60 ℃, and hydrolyzing for 5-9 h to obtain a collagen polypeptide hydrolysate;
(3) synthesis of organosilicon-collagen polypeptide antibacterial material
According to the molar ratio of (1-2) to 1 of epoxy polysiloxane quaternary ammonium salt to primary amino group in the collagen polypeptide hydrolysate, dripping the epoxy polysiloxane quaternary ammonium salt into the collagen polypeptide hydrolysate, and reacting for 2-8 hours under the condition of stirring at the temperature of 30-65 ℃; adjusting the pH value of the solution after reaction to be neutral; and (3) distilling under reduced pressure to remove 50-80% of water, and freeze-drying at-60 to-40 ℃ for 20-50 h to obtain the organic silicon-collagen polypeptide antibacterial material.
2. The method for preparing the organosilicon-collagen polypeptide antibacterial material according to claim 1, wherein the reaction temperature in the step (3) is 40-60 ℃.
3. The method for preparing the organosilicon-collagen polypeptide antibacterial material according to claim 1, wherein the step (3) is performed by freeze-drying and then reflux extraction with acetone solution for 65-80 h.
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