Anti-adhesion functional coating and preparation method and application thereof

Abstract

The present invention provides an anti-adhesion functional coating and a preparation method and application thereof. The preparation method of the anti-adhesion functional coating of the present invention comprises the following steps: S1: mixing amino silicone oil and dimethyl silicone oil to obtain a silicone oil mixture; S2: adding the silicone oil mixture dropwise to a gelatin aqueous solution, stirring and mixing, and then performing a cross-linking reaction to obtain a reaction liquid; S3: coating the reaction liquid on a substrate, curing, and obtaining an anti-adhesion functional coating. The anti-adhesion functional coating of the present invention has strong adhesion to the substrate and can be used as an ideal coating to prevent blood from adhering to form thrombi; at the same time, the anti-adhesion functional coating has extremely strong biosafety and can be extended to the inner coating of food bottles to prevent the adhesion of foods with high viscosity such as yogurt and ketchup, thereby reducing food loss and improving resource utilization.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to an anti-adhesion functional coating, its preparation method, and its application. Background Technology

[0002] Implantable medical devices and extracorporeal blood circulation devices have saved many lives, but both can lead to blood clots forming on their surfaces, endangering human health and medical outcomes. Thrombosis and bioaccumulation cause serious morbidity and mortality worldwide. In clinical practice, soluble anticoagulants such as heparin are commonly used to address thrombosis and bioaccumulation; however, heparin can cause secondary damage such as postoperative bleeding and thrombocytopenia.

[0003] Currently, the following methods are mainly used to create hydrophobic structures to achieve anti-blood adhesion functionality. The first method involves creating micro / nano-structured surfaces to achieve Cassie-Baxter hydrophobicity. However, these micro / nano-surfaces have poor mechanical properties, and the micro / nano particles can easily detach and enter the human body, forming blood clots and endangering human health. The second method involves grafting fluorinated organic compounds or silane segments to form monolayer hydrophobic compounds. However, the crosslinking agents, initiators, and solvents used in the grafting process are all toxic to humans, resulting in these hydrophobic compound coatings lacking good biocompatibility, making medical devices with such coatings unsuitable for medical applications. The third method involves infusing porous surfaces with a smooth liquid (SLIPS). This method can create anti-adhesion and anti-thrombotic coatings in a short period, but the liquid is prone to leakage and cannot maintain its performance in the long term.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide an anti-adhesion functional coating, its preparation method and application. The anti-adhesion functional coating has strong substrate adhesion, which can prevent blood from adhering and forming thrombi, and can also prevent highly viscous foods from adhering.

[0006] This invention provides a method for preparing an anti-adhesion functional coating, comprising the following steps:

[0007] S1: Mix amino silicone oil and dimethyl silicone oil to obtain a silicone oil mixture;

[0008] S2: Add the silicone oil mixture dropwise to the gelatin aqueous solution, stir and mix, and then carry out a cross-linking reaction to obtain the reaction solution;

[0009] S3: Apply the reaction solution to the substrate and cure it to obtain an anti-adhesion functional coating.

[0010] This invention uses gelatin and other protein materials that dissolve upon heating and solidify upon cooling as the coating matrix, amino silicone oil as the hydrophobic functional segment, and dimethyl silicone oil as the smoothing liquid for infusion, synthesizing a hydrophobic anti-adhesion functional coating in a one-pot process. The coating uses gelatin, a natural polymer compound, as the main matrix. Gelatin is a protein obtained by partial hydrolysis of collagen, and is inherently safe and non-toxic, suitable for applications in the medical and food industries. As a hydrophilic substance, gelatin swells in water and dissolves upon heating to form a light yellow, transparent gelatin aqueous solution. Because gelatin belongs to the protein macromolecule category, it has good biocompatibility as the coating matrix. The coating is formed by heating and stirring with water to form a solution, followed by cooling. The amino groups in the amino silicone oil react with the carboxyl groups in the gelatin macromolecules to generate amides, thereby crosslinking the hydrophobic silane segments onto the gelatin, giving the coating a stable anti-blood adhesion effect. Furthermore, the infusion of dimethyl silicone oil enhances the hydrophobic properties of the coating.

[0011] In this invention, amino silicone oils of different molecular weights and types can be selected; specifically, the amino silicone oil type is aminoethyl silicone oil or aminopropyl silicone oil, etc. This invention introduces amino silicone oil into the gelatin system. The carboxyl groups provided by amino acids can chemically react with substances containing amino groups to form amide bonds, crosslinking silane segments onto the gelatin macromolecules. The silicone oil segments of gelatin and amino silicone oil are crosslinked through amide bonds, eliminating the impact of toxic chemicals such as traditional organic crosslinking agents and initiators on the biocompatibility of the coating, and effectively solving the problem of non-toxic bonding between silicone oil segments and the hydrophilic substrate.

[0012] In this invention, dimethyl silicone oils with different viscosity coefficients can be used; specifically, the viscosity coefficient of the dimethyl silicone oil is 20-300 mPa·s. By adding dimethyl silicone oil to the gelatin system, due to the principle of similarity and miscibility between the silicone oil segment structures of dimethyl silicone oil and amino silicone oil, the dimethyl silicone oil can aggregate near the fixed amino silicone oil segments, thus achieving uniform mixing into the gelatin aqueous solution system. This system solves the problem of miscibility between silicone oil and water due to their different densities and properties, and innovatively uses water as a solvent, achieving zero pollution and zero loss of the solvent, effectively solving the problem of immiscibility between silicone oil and water.

[0013] In step S1, the ratio of amino silicone oil to dimethyl silicone oil in the silicone oil mixture can be varied according to actual needs; specifically, the mass ratio of amino silicone oil to dimethyl silicone oil can be (0.2-0.5):2.

[0014] In step S2, gelatin and water are stirred and mixed to obtain a gelatin aqueous solution. The ratio of gelatin to water can be varied according to actual needs; specifically, the mass ratio of gelatin to water can be 1:(3-10); the temperature during stirring is 40-70℃, and the stirring speed is 140-300 r / min. The mass ratio of silicone oil mixture to gelatin aqueous solution can be 1:(3-12). Furthermore, a crosslinking reaction can be carried out under stirring conditions, with a stirring speed of 140-300 r / min and a crosslinking reaction time of 1-5 h.

[0015] In step S3, the substrate is not strictly limited; a suitable substrate can be selected according to actual needs, such as polytetrafluoroethylene film, glass sheet, etc. In particular, the curing process of this invention includes sequential freezing, thawing, and drying, with a freezing time of 2-6 hours. This invention uses a simple freezing method to solidify the water in the system into ice. In the ice layer, gelatin fibers can spontaneously absorb the uncured dimethyl silicone oil liquid through capillary action, forming a uniform hydrophobic substance. Finally, drying the water yields an anti-adhesion functional coating. This coating has significant advantages such as strong adhesion to the substrate, solving the problem of coating-substrate adhesion.

[0016] The present invention also provides an anti-adhesion functional coating, which is prepared according to the above preparation method.

[0017] The present invention also provides the application of the above-mentioned anti-adhesion functional coating as a medical coating or a food coating.

[0018] This invention employs a one-pot method for the rapid preparation of a hydrophobic, anti-adhesion functional coating. The coating uses gelatin-amino silicone oil-dimethyl silicone oil as raw materials to synthesize a medical coating with anti-blood adhesion and good biocompatibility. The raw materials in this system are readily available and inexpensive, allowing for mass production. Gelatin itself is essentially harmless to the human body and can dissolve in aqueous solution by heating and then cooling to form a coating network. The amino groups in the amino silicone oil can react with the carboxyl groups on the gelatin. The dimethyl silicone oil and amino silicone oil segments are hydrophobic and harmless to the human body. The final coating can be safely used on medical devices, serving as an ideal coating to prevent blood adhesion and thrombosis. Furthermore, due to its excellent biocompatibility, this coating can be extended to the inner coating of food bottles, preventing adhesion of highly viscous foods such as yogurt and ketchup, thereby reducing food waste and improving resource utilization. Attached Figure Description

[0019] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0020] Figure 1 The image shows blood sliding off the coating surface of Example 1; where a: before sliding, b: after sliding.

[0021] Figure 2 The image shows the coagulation and detachment of blood on the coating surface of Example 1; where a: before detachment, b: after detachment;

[0022] Figure 3 The contact angles of water, blood, and edible oil on the coating of Example 1 are: a: water, b: blood, and c: edible oil.

[0023] Figure 4 The shear strength diagrams for the coating of Example 1 on different substrates are shown.

[0024] Figure 5 The image shows milk sliding off the coating surface of Example 1; where a: before sliding, b: after sliding.

[0025] Figure 6 The image shows cola sliding off the coating surface of Example 1; where a: before sliding, b: after sliding.

[0026] Figure 7 The image shows the yogurt sliding off the coating surface of Example 1; where a: before sliding, b: after sliding.

[0027] Figure 8 The image shows the tomato sauce sliding off the coating surface of Example 1; where a: before sliding, b: after sliding.

[0028] Figure 9 The image shows the honey sliding off the coating surface of Example 1; where a: before sliding, b: after sliding.

[0029] Figure 10 The image shows the oyster sauce sliding off the coating surface in Example 1; where a: before sliding, b: after sliding.

[0030] Figure 11 The image shows blood sliding off the coating surface of Control Example 1; where a: before sliding, b: after sliding.

[0031] Figure 12 The image shows the coagulation and detachment of blood on the coating surface of Control Example 1; where a: before detachment, b: after detachment;

[0032] Figure 13 The image shows blood sliding off the coating surface of Control Example 2; where a: before sliding, b: after sliding.

[0033] Figure 14 The image shows the coagulation and detachment of blood on the coating surface of Control Example 1; where a: before detachment, b: after detachment;

[0034] Figure 15 The image shows blood sliding off the coating surface of Control Example 3; where a: before sliding, b: after sliding. Detailed Implementation

[0035] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0036] It should be noted that the terminology used herein is for the purpose of describing particular implementations only and is not intended to limit the exemplary implementations according to this application. As used herein, the singular form includes the plural form unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this description, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0037] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0038] The raw materials for each embodiment are as follows:

[0039] Aminopropyl silicone oil: Mn=42773, Mw=95662, purchased from Maclean;

[0040] Dimethyl silicone oil: viscosity is 20 mPa·s.

[0041] Example 1

[0042] The method for preparing the anti-adhesion functional coating in this embodiment includes the following steps:

[0043] S1: Preparation of a mixture of gelatin aqueous solution and silicone oil

[0044] Add 3g of gelatin and 20mL of water to a 100mL double-necked flask, and stir at 150r / min in an oil bath at 45℃ to dissolve the gelatin solution.

[0045] Add 0.5g of amino silicone oil and 2g of dimethyl silicone oil to a glass bottle, place it on a magnetic stirrer and stir for 5 minutes to obtain a uniformly dispersed silicone oil mixture.

[0046] S2: Reaction

[0047] The silicone oil mixture was drawn into the gelatin aqueous solution in a double-necked flask using a dropper. The mixture was stirred at 150 rpm for 10 min to completely disperse the silicone oil mixture in the gelatin aqueous solution. Then, the crosslinking reaction was carried out at 150 rpm for 4 h to obtain the reaction solution.

[0048] S3: Coating preparation

[0049] The reaction solution was coated onto a glass slide, and the reaction solution solidified at room temperature. Then, it was quickly placed in the freezer compartment of a refrigerator and frozen for 3 hours. After freezing, the product was removed, thawed at room temperature, and dried to obtain an anti-adhesion functional coating.

[0050] Example 2

[0051] The method for preparing the anti-adhesion functional coating in this embodiment includes the following steps:

[0052] S1: Preparation of a mixture of gelatin aqueous solution and silicone oil

[0053] Add 3g of gelatin and 15mL of water to a 100mL double-necked flask, and stir at 160r / min in a 50℃ oil bath to dissolve the gelatin solution.

[0054] Add 0.2g of amino silicone oil and 2g of dimethyl silicone oil to a glass bottle, place it on a magnetic stirrer and stir for 5 minutes to obtain a uniformly dispersed silicone oil mixture.

[0055] S2: Reaction

[0056] The silicone oil mixture was drawn into the gelatin aqueous solution in a double-necked flask using a dropper. The mixture was stirred at 160 rpm for 10 min to completely disperse the silicone oil mixture in the gelatin aqueous solution. Then, the crosslinking reaction was carried out at 160 rpm for 3 h to obtain the reaction solution.

[0057] S3: Coating preparation

[0058] The reaction solution was coated onto a glass slide, and the reaction solution solidified at room temperature. Then, it was quickly placed in the freezer compartment of a refrigerator and frozen for 2 hours. After freezing, the product was removed, thawed at room temperature, and dried to obtain an anti-adhesion functional coating.

[0059] Example 3

[0060] The method for preparing the anti-adhesion functional coating in this embodiment includes the following steps:

[0061] S1: Preparation of a mixture of gelatin aqueous solution and silicone oil

[0062] Add 3g of gelatin and 30mL of water to a 100mL double-necked flask, and stir at 140r / min in an oil bath at 555℃ to dissolve the gelatin solution.

[0063] Add 0.3g of amino silicone oil and 2g of dimethyl silicone oil to a glass bottle, place it on a magnetic stirrer and stir for 5 minutes to obtain a uniformly dispersed silicone oil mixture.

[0064] S2: Reaction

[0065] The silicone oil mixture was drawn into the gelatin aqueous solution in a double-necked flask using a dropper. The mixture was stirred at 140 rpm for 10 min to completely disperse the silicone oil mixture in the gelatin aqueous solution. Then, the crosslinking reaction was carried out at 140 rpm for 5 h to obtain the reaction solution.

[0066] S3: Coating preparation

[0067] The reaction solution was coated onto a glass slide, and the reaction solution solidified at room temperature. Then, it was quickly placed in the freezer compartment of a refrigerator and frozen for 4 hours. After freezing, the product was removed, thawed at room temperature, and dried to obtain an anti-adhesion functional coating.

[0068] Compare with Example 1

[0069] Except for replacing the amino silicone oil in Example 1 with vinyl silicone oil, the rest is basically the same as in Example 1.

[0070] Compare with Example 2

[0071] Except for replacing the dimethyl silicone oil in Example 1 with fluoroether, the rest is basically the same as in Example 1.

[0072] Compare with Example 3

[0073] Except for replacing the gelatin in Example 1 with carboxymethyl chitosan, the rest is basically the same as in Example 1.

[0074] Experimental Example 1

[0075] Blood was dropped onto the coating of Example 1, and the blood dripping off the coating surface is shown in the figure. Figure 1 (Slippage time 30s); by Figure 1 It is evident that blood can slide cleanly and completely off the coating without adhering to it.

[0076] A blood scab peeling test was performed on the coating of Example 1. The image shows the coagulation and peeling of blood on the surface of the coating of Example 1. Figure 2 ;Depend on Figure 2 It is evident that the blood scab can be completely peeled off from the coating, indicating that the coating has a very good anti-blood adhesion effect.

[0077] Contact angles of water, blood, and edible oil on the coating are shown in the figure. Figure 3 ;Depend on Figure 3 It is evident that the coating exhibits excellent hydrophobicity.

[0078] The shear strength diagrams of the coating and different substrates in Example 1 are shown below. Figure 4 ;Depend on Figure 4 It is evident that the coating has strong adhesion to each substrate and will not easily peel off.

[0079] Figures 1-4 This demonstrates that the coating of Example 1 can be safely used on medical devices, serving as an ideal medical coating to prevent blood adhesion and thrombus formation.

[0080] Experimental Example 2

[0081] Milk, cola, yogurt, ketchup, honey, and oyster sauce were respectively dripped onto the coating of Example 1, and their respective drop patterns are shown in the figure. Figures 5-10 .

[0082] Figures 5-10 This demonstrates that the coating of Example 1 can prevent food such as milk, cola, yogurt, ketchup, honey, and oyster sauce from adhering to the food. Therefore, it can be extended to the inner coating of food bottles to prevent the adhesion of highly viscous foods, reduce food loss, and improve resource utilization.

[0083] Experimental Example 3

[0084] Blood was dropped onto the coatings of Control Examples 1-3, and the blood slippage (slippage time 30s) and coagulation / detachment patterns on the surfaces of each coating are shown in the figures below. Figures 11-15 .

[0085] Figure 11 , Figure 12 This indicates that, compared to amino silicone oil, the coating in Comparative Example 1, made with vinyl silicone oil, cannot graft onto gelatin chains because the vinyl groups do not react with gelatin, leaving residual vinyl groups that are harmful to the human body. Furthermore, neither vinyl silicone oil nor dimethyl silicone oil can be fixed onto gelatin molecular chains, making them prone to performance loss. Therefore, the coating in Comparative Example 1 is insufficient to prevent blood from slipping off. Figure 11 Meanwhile, the blood clots adhered to the coating surface of Control Example 1 and could not be peeled off. Figure 12 ).

[0086] Figure 13 , Figure 14 This indicates that the coating in Comparative Example 2 used fluoroether as an anti-adhesion coating. Although fluoroether is a commonly used smooth liquid, compared to dimethyl silicone oil, it poses certain biological hazards to the human body and is unsuitable for use as a medical coating material or in food applications. Furthermore, fluoroether lacks silane segments and cannot aggregate near the reactive amino silicone oil segments, easily volatilizing and losing its properties. Therefore, the coating performance of Comparative Example 2 is insufficient to prevent blood from slipping off. Figure 13 Meanwhile, the blood clots will adhere to the coating surface and cannot be peeled off. Figure 14 ).

[0087] Figure 15 This indicates that the coating of Control Example 3 is not as fast as gelatin in terms of dissolving upon heating and reducing coagulation, requiring more time; a blood slip test revealed that blood adhered to the coating of Control Example 3. Figure 15 ).

[0088] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an anti-adhesion functional coating, characterized in that: The steps include: S1: Mixing amino silicone oil and dimethyl silicone oil to obtain a silicone oil mixture; S2: adding the silicone oil mixture dropwise to the gelatin aqueous solution, stirring and mixing, and then performing a cross-linking reaction to obtain a reaction solution; S3: coating the reaction solution on the substrate and curing it to obtain an anti-adhesion functional coating; Among them, the mass ratio of amino silicone oil to dimethyl silicone oil is (0.2-0.5):2; the mass ratio of silicone oil mixture to gelatin aqueous solution is 1:(3-12); and the viscosity coefficient of dimethyl silicone oil is 20-300 mpa·s.

2. The preparation method according to claim 1, characterized in that: The gelatin and water are stirred and mixed to prepare a gelatin aqueous solution.

3. The preparation method according to claim 2, characterized in that: The mass ratio of gelatin to water is 1:(2-10).

4. The preparation method according to claim 1, characterized in that The cross-linking reaction is carried out under stirring conditions, the stirring speed is 140-300 r / min, and the cross-linking reaction time is 1-5 h.

5. The preparation method according to claim 1, characterized in that: Curing involves sequential freezing, thawing and drying.

6. The preparation method according to claim 5, characterized in that The freezing time is 2-6 h.

7. An anti-adhesion functional coating, characterized in that: Prepared according to any one of the preparation methods of claims 1-6.

8. Use of the anti-adhesion functional coating according to claim 7 as a medical coating or a food coating.

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