Medical water-absorbing composite material and preparation method thereof

Abstract

The invention discloses a medical water-absorbing composite material and a preparation method thereof, and relates to the technical field of non-woven fabrics. The preparation method comprises the following steps: by taking bismuth nitrate, butyl titanate and the like as raw materials, performing electrospinning and gradient calcining treatment to form piezoelectric ceramic non-woven fabric; then glycolic acid and 2-amino-4-hydroxy-1, 4-succinic acid are polymerized to form a polyester compound, the composite material is effectively prevented from being adhered to a wound, the polyester compound serves as a wall material, chitosan serves as a core material and is sprayed and deposited on the surface of non-woven fabric, when the super absorbent resin on the other side absorbs water and expands, the microcapsules and the piezoelectric ceramic are extruded at the same time, the chitosan is released, and the wound healing effect is achieved. Oxygen is generated to promote wound healing; then modifying a polypropylene non-woven fabric by utilizing methyl 2-hydroxybutyrate, hydrazine hydrate, 1-(dimethylamino)-2-methyl-3-pentanone and 4-((6-bromohexyl) oxy)-2-hydroxybenzaldehyde to form an antibacterial non-woven fabric, and attaching the antibacterial non-woven fabric to the surface of the super absorbent resin. The medical water-absorbing composite material prepared by the invention has the effects of resisting bacteria and promoting wound healing.

Description

Technical Field

[0001] The invention relates to the technical field of nonwoven fabrics, in particular to a medical water-absorbing composite material and a preparation method thereof. Background Art

[0002] Non-woven fabric is a kind of fabric that does not require spinning and weaving, and is composed of directional or random fibers. It simply arranges textile short fibers or filaments in a directional or random manner to form a fiber mesh structure, and then uses mechanical, thermal bonding or chemical methods to reinforce it. Non-woven fabrics are moisture-proof, breathable, flexible, lightweight, non-combustible, easy to decompose, non-toxic and non-irritating, rich in colors, low in price, and recyclable.

[0003] With the progress of materials science and technology, the research of medical dressings has also achieved rapid development. Traditional emergency wound dressings are mainly cotton products and non-woven fabrics. Although cotton dressings and non-woven fabrics have the characteristics of strong water absorption, good heat resistance, and excellent alkali resistance, they are also easy to adhere to the wound surface and cause secondary trauma. At the same time, because they are inert dressings, they have no obvious effect on promoting the healing of the wound surface. In addition, the existing non-woven fabric materials have weak antibacterial effects, cannot prevent bacteria from contacting the wound, and cannot effectively prevent bacterial reproduction and infection and cross infection. Summary of the invention

[0004] The purpose of the present invention is to provide a medical water-absorbent composite material and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a medical water-absorbent composite material, comprising a repair non-woven fabric layer, a water-absorbent resin layer, and an antibacterial non-woven fabric layer.

[0006] Furthermore, the repair non-woven fabric layer is prepared by the following method: bismuth nitrate pentahydrate, barium acetate, lead acetate trihydrate, lanthanum acetate, ethylene glycol monomethyl ether, acetic acid, and acetylacetone are mixed, stirred and dissolved, and then a butyl titanate solution is added, and the precursor solution A is concentrated to obtain a precursor solution A; a polyvinylpyrrolidone solution is added to the precursor solution A to obtain a spinnable sol, and after electrospinning, the sol is dried for a period of time, and then the piezoelectric ceramic non-woven fabric is heated by gradient heating to obtain a piezoelectric ceramic non-woven fabric; microcapsules are sprayed on the piezoelectric ceramic non-woven fabric, and heat treatment is performed to obtain a repair non-woven fabric layer.

[0007] Furthermore, the microcapsules are prepared by the following method: hydroxyacetic acid, 2-amino-4-hydroxy-1,4-succinic acid, magnesium acetate, potassium acetate, and acetic anhydride are mixed and heated in a gradient manner to obtain a polyester compound; the polyester compound and chloroform are ultrasonically mixed, a Span solution is added, ultrasonication is continued, chitosan is added, ultrasonication is continued, a Tween mixture is added, high-speed stirring is performed, and ultrasonication is continued.

[0008] Furthermore, the antibacterial non-woven fabric layer is prepared by the following method: treating a polypropylene non-woven fabric with plasma to obtain a pretreated non-woven fabric; placing the pretreated non-woven fabric in a 2-hydroxybutyric acid methyl ester solution, soaking it for a period of time, and then esterifying the non-woven fabric; mixing the esterified non-woven fabric, hydrazine hydrate, anhydrous ethanol, and deionized water, and heating it to obtain a hydrazide non-woven fabric; mixing the hydrazide non-woven fabric, 1-(dimethylamino)-2-methyl-3-pentanone, and anhydrous ethanol, and heating it to obtain an acylhydrazone compound; and mixing the acylhydrazone compound, 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde, and cyclohexane to obtain an antibacterial non-woven fabric.

[0009] Furthermore, a method for preparing a medical water-absorbent composite material comprises the following preparation steps:

[0010] (1) bismuth nitrate pentahydrate, barium acetate, lead acetate trihydrate, lanthanum acetate, ethylene glycol monomethyl ether, acetic acid, and acetylacetone are mixed in a mass ratio of 1:0.6:1.5:0.1:4.8:3.6:0.1 to 1:0.8:2.4:0.2:7.6:6.0:0.1, stirred and dissolved, and then a butyl titanate solution with a mass of 2.5 to 4.0 times that of barium acetate is added, stirred evenly, and concentrated at 65° C. for 29 to 41 minutes to obtain a precursor solution A; and a polyvinylpyrrolidone solution with a mass of 0.6 to 0.7 times that of the precursor solution A is added to the precursor solution A, and stirred evenly to obtain a spinnable sol;

[0011] (2) electrospinning the spinnable sol at an applied voltage of 22 kV and a receiving distance of 22 cm, drying at 90° C. for 40 to 50 h, heating to 500° C., keeping the temperature for 30 to 40 min, heating to 700° C., keeping the temperature for 50 to 70 min, heating to 1000° C., keeping the temperature for 100 to 120 min, and obtaining a piezoelectric ceramic nonwoven fabric;

[0012] (3) Mix microcapsules, 3-chloropropyltriethoxysilane, anhydrous ethanol and deionized water in a mass ratio

[0013] 1:0.5:8.5:0.4~1:1.0:9.7:0.5, stirring at 100rpm for 1~3h to obtain a microcapsule solution; spraying the microcapsule solution of 0.2~0.4 times the mass of the piezoelectric ceramic non-woven fabric onto the piezoelectric ceramic non-woven fabric, treating at 100℃ for 58~70min, cooling to room temperature, washing with anhydrous ethanol for 4~6 times to obtain a repaired non-woven fabric layer;

[0014] (4) After the super absorbent resin is heated at 120° C. until it melts, carboxyl-terminated nitrile rubber, polyamide 651, and KH-550 are added in a mass ratio of 1:5:10, and the mass ratio of the toughening agent to the super absorbent resin is 0.01:1, and the mixture is stirred evenly to obtain a water-absorbent resin solution; the water-absorbent resin solution in an amount of 0.1 to 0.3 times the mass of the repair non-woven fabric layer is sprayed onto the repair non-woven fabric layer, and an antibacterial non-woven fabric of the same area as the repair non-woven fabric layer is attached, and the mixture is cured at 180° C. for 3 to 5 hours to obtain a medical absorbent composite material.

[0015] Furthermore, the butyl titanate solution in step (1) is a mixture of butyl titanate, anhydrous ethanol and lactic acid in a mass ratio of 1:1.2:0.2; and the polyvinyl pyrrolidone solution is a mixture of polyvinyl pyrrolidone and anhydrous ethanol in a mass ratio of 1:2.4.

[0016] Furthermore, the preparation method of the microcapsules in step (3) is as follows: the polyester compound and chloroform are mixed in a mass ratio of 1:296, and after ultrasonication at 25kHz for 28 to 44 minutes, a Span solution with a mass ratio of 28 to 32 times the mass of the polyester compound is added, wherein the mass ratio of Span 80 to chloroform in the Span solution is 1:8, and after ultrasonication for 30 to 44 minutes, chitosan with a mass ratio of 0.8 to 1.8 times the mass of the polyester compound is added, and after ultrasonication for 12 to 26 minutes, a Tween mixed solution with a mass ratio of 2040 times the mass of the polyester compound is added, wherein the mass ratio of Tween-80, polyvinyl alcohol and deionized water in the Tween mixed solution is 1:1:100, and after stirring at 1000rpm for 10 to 18 minutes, ultrasonication is continued for 4 to 5 hours.

[0017] Furthermore, the preparation method of the polyester compound is: hydroxyacetic acid, 2-amino-4-hydroxy-1,4-butanedioic acid, magnesium acetate, potassium acetate, and acetic anhydride are mixed in a mass ratio of 1:0.5:0.005:0.005:7 to 1:0.7:0.005:0.005:14, react at 151°C for 2.5 to 4 hours under a nitrogen atmosphere, heat to 222°C, keep warm for 2 to 4 hours, heat to 248°C, keep warm for 2 to 4 hours, evacuate for 15 to 29 minutes, cool to room temperature, take out, wash with acetone 4 to 6 times, and dry at 80°C and a vacuum degree of 0.1 MPa for 7.5 to 9 hours.

[0018] Furthermore, the preparation method of the bacterial nonwoven fabric in step (4) is:

[0019] a. Place the pretreated nonwoven fabric in a 2-hydroxybutyric acid methyl ester solution with a mass of 5 to 10 times that of the pretreated nonwoven fabric, wherein the mass ratio of 2-hydroxybutyric acid methyl ester to Tris buffer in the 2-hydroxybutyric acid methyl ester solution is 1:0.68, soak for 1 to 3 hours, take out, wash with deionized water for 5 to 7 times, and dry at 60°C and a vacuum degree of 0.1 MPa for 4 to 6 hours to obtain an esterified nonwoven fabric; mix the esterified nonwoven fabric, hydrazine hydrate, anhydrous ethanol, and deionized water in a mass ratio of 1:0.6:88:3 to 1:0.8:96:6, heat at 60 rpm and 60°C for 6 to 9.5 hours, heat to 90°C, heat for 2 to 4 hours, take out, wash with deionized water and ethyl acetate for 6 to 8 times in sequence, and dry at 60°C for 8 to 10 hours to obtain a hydrazide nonwoven fabric;

[0020] b. Mix hydrazide non-woven fabric, 1-(dimethylamino)-2-methyl-3-pentanone and anhydrous ethanol in a mass ratio of 1:0.5:77 to 1:0.8:109, react at 60°C for 7 to 10 hours, take out, and wash with deionized water for 5 to 7 times to obtain an acylhydrazone compound; at 45°C, mix the acylhydrazone compound, 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde and cyclohexane in a mass ratio of 1:0.4:6 to 1:0.7:12, react for 11 to 14 hours, cool to room temperature, stand for 7 to 10 hours, take out, wash with anhydrous ethanol for 8 to 10 times, then wash with deionized water for 4 to 6 times, and dry at 60°C for 8 to 10 hours to obtain an antibacterial non-woven fabric.

[0021] Furthermore, the preparation method of the pretreated nonwoven fabric in step a is: 2 The polypropylene nonwoven fabric was placed in a plasma device, and argon and oxygen were introduced at a flow ratio of 17:3, and treated at 60W for 4 to 10 minutes.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] The medical water-absorbing composite material prepared by the invention comprises a repair non-woven fabric layer, a water-absorbing resin layer and an antibacterial non-woven fabric layer, so as to achieve the effects of promoting wound healing and inhibiting bacteria.

[0024] Firstly, the present invention performs electrospinning treatment, uses bismuth nitrate, butyl titanate and the like as raw materials, obtains a spinnable sol, and obtains nanofibers through electrospinning; then performs gradient calcination treatment, the ceramic grains in the nanofibers gradually grow, overlap each other to form an inorganic skeleton, obtains a piezoelectric ceramic non-woven fabric, and forms pores between the fibers, which is beneficial to the transmission of water molecules and improves the high water absorption of the composite material; then, hydroxyacetic acid and 2-amino-4-hydroxy-1,4-succinic acid are polymerized to form a polyester compound, and due to the flexibility of hydroxyacetic acid and 2-amino-4-hydroxy-1,4-succinic acid, the water-absorbing composite material can be effectively prevented from adhering to the wound, which is beneficial to promoting wound healing. This is a wall material with chitosan as the core material. The first spraying treatment is carried out and deposited on the surface of the non-woven fabric to form a skin-friendly side. Then the second spraying treatment is carried out and a highly absorbent resin is sprayed on the other side of the non-woven fabric. When it absorbs water and swells into a hydrogel, it squeezes the microcapsules, causing the wall material to rupture while squeezing the electric ceramic non-woven fabric to generate electric charges, which react with water molecules to generate hydroxyl free radicals, thereby oxidatively degrading the polyester compound macromolecular chains, further expanding the pores of the wall material, releasing chitosan, and promoting wound healing. In the degradation process, oxygen is generated to increase the activity of fibroblasts, which is beneficial to the synthesis of collagen in epithelial tissue and the growth of epidermal cells, thereby promoting wound healing.

[0025] Secondly, the antibacterial non-woven fabric layer uses polypropylene non-woven fabric as raw material, firstly uses oxygen plasma to modify its surface, introduces active groups, and the hydroxyl group of methyl 2-hydroxybutyrate reacts with the active group and is grafted on the surface of polypropylene non-woven fabric. The methyl ester of methyl 2-hydroxybutyrate reacts with hydrazine hydrate to form a hydrazide compound; the amino group of the hydrazide compound reacts with the keto group of 1-(dimethylamino)-2-methyl-3-pentanone to form an acylhydrazone compound, which has good antibacterial activity, so that the composite material has an antibacterial effect; 1-(dimethylamino)-2-methyl The amino group of 3-pentanone reacts with the bromide ion of 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde to form a quaternary ammonium salt cationic antibacterial group, which synergizes with the acylhydrazone group to enhance the antibacterial property of the composite material. In addition, hydrophobic groups such as methyl and long-chain alkyl are perpendicular to the surface of the non-woven fabric to form a hydrophobic barrier layer, which can block the invasion of microorganisms and is beneficial to improving the antibacterial property of the composite material. At the same time, the hydroxyl groups of the antibacterial non-woven fabric layer can react with the active groups of the water-absorbing resin layer to make the two tightly cross-linked, thereby improving the antibacterial property of the composite material. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0027] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the index testing methods of the medical water-absorbent composite material and the antibacterial non-woven fabric prepared in the following examples are as follows:

[0028] Promoting wound healing: After the hair on the back of SD rats was clipped, the rats were depilated with 4% sodium sulfide by mass, washed with warm water, and dried. The next day, 0.8 mL / 100 g of 5% chloral hydrate was injected intraperitoneally under anesthesia. Routine disinfection and draping were carried out on both sides of the back spine at 1 cm. An incision of about 5 cm was made parallel to the spine. The skin and subcutaneous tissue were cut deep into the muscle layer. If there was slight bleeding, the rats were wiped with sterile cotton balls to stop bleeding, and then sutured with 3-0 silk thread with a corner needle. The rats were returned to the mouse box and fed normally for 7 days after they were fully awake. The wounds were covered with the samples of the embodiment and the comparative example, and the recovery and adhesion were observed.

[0029] Antibacterial property: The antibacterial rate of the antibacterial nonwoven fabrics of the embodiment and the comparative example was tested according to GB / T 20944.3.

[0030] Example 1

[0031] (1) bismuth nitrate pentahydrate, barium acetate, lead acetate trihydrate, lanthanum acetate, ethylene glycol monomethyl ether, acetic acid, and acetylacetone are mixed in a mass ratio of 1:0.6:1.5:0.1:4.8:3.6:0.1, stirred and dissolved, and then a butyl titanate solution with a mass ratio of 2.5 times that of the barium acetate is added, wherein the mass ratio of butyl titanate, anhydrous ethanol, and lactic acid in the butyl titanate solution is 1:1.2:0.2, stirred evenly, and concentrated at 65° C. for 29 minutes to obtain a precursor solution A; a polyvinyl pyrrolidone solution with a mass ratio of 0.6 times that of the precursor solution A is added to the precursor solution A, wherein the mass ratio of polyvinyl pyrrolidone to anhydrous ethanol in the polyvinyl pyrrolidone solution is 1:2.4, and stirred evenly to obtain a spinnable sol;

[0032] (2) electrospinning the spinnable sol at an applied voltage of 22 kV and a receiving distance of 22 cm, drying at 90° C. for 40 h, heating to 500° C., keeping the temperature for 30 min, heating to 700° C., keeping the temperature for 50 min, heating to 1000° C., keeping the temperature for 100 min, and obtaining a piezoelectric ceramic nonwoven fabric;

[0033] (3) Hydroxyacetic acid, 2-amino-4-hydroxy-1,4-butanedioic acid, magnesium acetate, potassium acetate, and acetic anhydride were mixed in a mass ratio of 1:0.5:0.005:0.005:7, reacted at 151° C. for 2.5 h under a nitrogen atmosphere, heated to 222° C., kept warm for 2 h, heated to 248° C., kept warm for 2 h, evacuated for 15 min, cooled to room temperature, taken out, washed with acetone four times, and dried at 80° C. and a vacuum degree of 0.1 MPa for 7.5 h to obtain a polyester compound;

[0034] (4) The polyester compound and chloroform were mixed in a mass ratio of 1:296, and after ultrasonication at 25kHz for 28 minutes, a Span solution with a mass ratio of 28 times the mass of the polyester compound was added, wherein the mass ratio of Span 80 to chloroform in the Span solution was 1:8, and ultrasonication was continued for 30 minutes, and chitosan with a mass ratio of 0.8 times the mass of the polyester compound was added, and ultrasonication was continued for 12 minutes, and then a Tween mixed solution with a mass ratio of 2040 times the mass of the polyester compound was added, wherein the mass ratio of Tween-80, polyvinyl alcohol and deionized water in the Tween mixed solution was 1:1:100, and the mixture was stirred at 1000 rpm for 10 minutes, and ultrasonication was continued for 4 hours to obtain microcapsules;

[0035] (5) Mixing microcapsules, 3-chloropropyltriethoxysilane, anhydrous ethanol, and deionized water in a mass ratio of 1:0.5:8.5:0.4, and stirring at 100 rpm for 1 hour to obtain a microcapsule solution; spraying the microcapsule solution in an amount of 0.2 times the mass of the piezoelectric ceramic non-woven fabric onto the piezoelectric ceramic non-woven fabric, treating at 100° C. for 58 minutes, cooling to room temperature, and washing with anhydrous ethanol for 4 times to obtain a repaired non-woven fabric layer;

[0036] (6) Set the weight to 40g / m 2 The polypropylene nonwoven fabric was placed in a plasma device, argon and oxygen were introduced at a flow ratio of 17:3, and the pretreated nonwoven fabric was treated at 60W for 4 minutes to obtain a pretreated nonwoven fabric; the pretreated nonwoven fabric was placed in a 2-hydroxybutyric acid methyl ester solution with a mass ratio of 5 times the mass of the pretreated nonwoven fabric, and the mass ratio of 2-hydroxybutyric acid methyl ester and Tris buffer in the 2-hydroxybutyric acid methyl ester solution was 1:0.68. After soaking for 1 hour, it was taken out, washed with deionized water 5 times, and dried at 60°C and a vacuum degree of 0.1MPa for 4 hours to obtain an esterified nonwoven fabric; the esterified nonwoven fabric, hydrazine hydrate, anhydrous ethanol, and deionized water were mixed at a mass ratio of 1:0.6:88:3, heated at 60rpm and 60°C for 6 hours, then heated to 90°C, heated for 2 hours, taken out, washed with deionized water and ethyl acetate 6 times in sequence, and dried at 60°C for 8 hours to obtain a hydrazide nonwoven fabric;

[0037] (7) Hydrazide non-woven fabric, 1-(dimethylamino)-2-methyl-3-pentanone, and anhydrous ethanol were mixed in a mass ratio of 1:0.5:77, reacted at 60°C for 7 hours, taken out, and washed with deionized water 5 times to obtain an acylhydrazone compound; at 45°C, the acylhydrazone compound, 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde, and cyclohexane were mixed in a mass ratio of 1:0.4:6, reacted for 11 hours, cooled to room temperature, allowed to stand for 7 hours, taken out, washed with anhydrous ethanol 8 times, and then washed with deionized water 4 times, and dried at 60°C for 8 hours to obtain an antibacterial non-woven fabric;

[0038] (8) After the super absorbent resin is heated at 120° C. until it melts, carboxyl-terminated nitrile rubber, polyamide 651, and KH-550 are added in a mass ratio of 1:5:10, and the mass ratio of the toughening agent to the super absorbent resin is 0.01:1, and the mixture is stirred evenly to obtain a water-absorbent resin solution; the water-absorbent resin solution in an amount 0.1 times the mass of the repair non-woven fabric layer is sprayed onto the repair non-woven fabric layer, and an antibacterial non-woven fabric of the same area as the repair non-woven fabric layer is attached, and the mixture is cured at 180° C. for 3 h to obtain a medical absorbent composite material.

[0039] Example 2

[0040] (1) bismuth nitrate pentahydrate, barium acetate, lead acetate trihydrate, lanthanum acetate, ethylene glycol monomethyl ether, acetic acid, and acetylacetone are mixed in a mass ratio of 1:0.7:1.9:0.15:6.2:4.8:0.1, stirred and dissolved, and then a butyl titanate solution with a mass ratio of 3.3 times that of the barium acetate is added, wherein the mass ratio of butyl titanate, anhydrous ethanol, and lactic acid in the butyl titanate solution is 1:1.2:0.2, stirred evenly, and concentrated at 65° C. for 35 min to obtain a precursor solution A; a polyvinyl pyrrolidone solution with a mass ratio of 0.65 times that of the precursor solution A is added to the precursor solution A, wherein the mass ratio of polyvinyl pyrrolidone to anhydrous ethanol in the polyvinyl pyrrolidone solution is 1:2.4, and stirred evenly to obtain a spinnable sol;

[0041] (2) electrospinning the spinnable sol at an applied voltage of 22 kV and a receiving distance of 22 cm, drying at 90° C. for 45 h, heating to 500° C., keeping the temperature for 35 min, heating to 700° C., keeping the temperature for 60 min, heating to 1000° C., keeping the temperature for 110 min, and obtaining a piezoelectric ceramic nonwoven fabric;

[0042] (3) Hydroxyacetic acid, 2-amino-4-hydroxy-1,4-butanedioic acid, magnesium acetate, potassium acetate, and acetic anhydride were mixed in a mass ratio of 1:0.6:0.005:0.005:10.5, reacted at 151° C. for 3.3 h under a nitrogen atmosphere, heated to 222° C., kept warm for 3 h, heated to 248° C., kept warm for 3 h, evacuated for 22 min, cooled to room temperature, taken out, washed with acetone 5 times, and dried at 80° C. and a vacuum degree of 0.1 MPa for 8.2 h to obtain a polyester compound;

[0043] (4) The polyester compound and chloroform were mixed in a mass ratio of 1:296, and after ultrasonication at 25kHz for 36 minutes, a Span solution 30 times the mass of the polyester compound was added, and the mass ratio of Span 80 to chloroform in the Span solution was 1:8. After ultrasonication for 37 minutes, chitosan 1.3 times the mass of the polyester compound was added. After ultrasonication for 19 minutes, a Tween mixture 2040 times the mass of the polyester compound was added, and the mass ratio of Tween-80, polyvinyl alcohol and deionized water in the Tween mixture was 1:1:100. After stirring at 1000 rpm for 14 minutes, ultrasonication was continued for 4.5 hours to obtain microcapsules;

[0044] (5) Mixing microcapsules, 3-chloropropyltriethoxysilane, anhydrous ethanol, and deionized water in a mass ratio of 1:0.75:9.1:0.45, and stirring at 100 rpm for 2 hours to obtain a microcapsule solution; spraying the microcapsule solution in an amount 0.3 times the mass of the piezoelectric ceramic non-woven fabric onto the piezoelectric ceramic non-woven fabric, treating at 100° C. for 64 minutes, cooling to room temperature, and washing with anhydrous ethanol for 5 times to obtain a repaired non-woven fabric layer;

[0045] (6) Set the weight to 50g / m 2 The polypropylene non-woven fabric was placed in a plasma device, argon and oxygen were introduced at a flow ratio of 17:3, and the pre-treated non-woven fabric was treated at 60W for 7 minutes to obtain a pre-treated non-woven fabric; the pre-treated non-woven fabric was placed in a 2-hydroxybutyric acid methyl ester solution with a mass ratio of 7.5 times the mass of the pre-treated non-woven fabric, and the mass ratio of 2-hydroxybutyric acid methyl ester and Tris buffer in the 2-hydroxybutyric acid methyl ester solution was 1:0.68. After soaking for 2 hours, it was taken out, washed with deionized water for 6 times, and dried at 60°C and a vacuum degree of 0.1MPa for 5 hours to obtain an esterified non-woven fabric; the esterified non-woven fabric, hydrazine hydrate, anhydrous ethanol, and deionized water were mixed at a mass ratio of 1:0.7:92:4.5, heated at 60rpm and 60°C for 7.8 hours, and then heated to 90°C, heated for 3 hours, taken out, washed with deionized water and ethyl acetate for 7 times in sequence, and dried at 60°C for 9 hours to obtain a hydrazide non-woven fabric;

[0046] (7) Hydrazide non-woven fabric, 1-(dimethylamino)-2-methyl-3-pentanone, and anhydrous ethanol were mixed in a mass ratio of 1:0.65:93, reacted at 60°C for 8.5 hours, taken out, and washed with deionized water 6 times to obtain an acylhydrazone compound; at 45°C, the acylhydrazone compound, 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde, and cyclohexane were mixed in a mass ratio of 1:0.55:9, reacted for 12.5 hours, cooled to room temperature, allowed to stand for 8.5 hours, taken out, washed with anhydrous ethanol 9 times, then washed with deionized water 5 times, and dried at 60°C for 9 hours to obtain an antibacterial non-woven fabric;

[0047] (8) After the super absorbent resin is heated at 120° C. until it melts, carboxyl-terminated nitrile rubber, polyamide 651, and KH-550 are added in a mass ratio of 1:5:10, and the mass ratio of the toughening agent to the super absorbent resin is 0.01:1, and the mixture is stirred evenly to obtain a water-absorbent resin solution; the water-absorbent resin solution in an amount of 0.2 times the mass of the repair non-woven fabric layer is sprayed onto the repair non-woven fabric layer, and an antibacterial non-woven fabric of the same area as the repair non-woven fabric layer is attached, and the mixture is cured at 180° C. for 4 h to obtain a medical absorbent composite material.

[0048] Example 3

[0049] (1) bismuth nitrate pentahydrate, barium acetate, lead acetate trihydrate, lanthanum acetate, ethylene glycol monomethyl ether, acetic acid, and acetylacetone are mixed in a mass ratio of 1:0.8:2.4:0.2:7.6:6.0:0.1, stirred and dissolved, and then a butyl titanate solution with a mass ratio of 4 times that of the barium acetate is added, wherein the mass ratio of butyl titanate, anhydrous ethanol, and lactic acid in the butyl titanate solution is 1:1.2:0.2, stirred evenly, and concentrated at 65° C. for 41 minutes to obtain a precursor solution A; a polyvinyl pyrrolidone solution with a mass ratio of 0.7 times that of the precursor solution A is added to the precursor solution A, wherein the mass ratio of polyvinyl pyrrolidone to anhydrous ethanol in the polyvinyl pyrrolidone solution is 1:2.4, and stirred evenly to obtain a spinnable sol;

[0050] (2) electrospinning the spinnable sol at an applied voltage of 22 kV and a receiving distance of 22 cm, drying at 90° C. for 50 h, heating to 500° C., keeping the temperature for 40 min, heating to 700° C., keeping the temperature for 70 min, heating to 1000° C., keeping the temperature for 120 min, and obtaining a piezoelectric ceramic nonwoven fabric;

[0051] (3) Hydroxyacetic acid, 2-amino-4-hydroxy-1,4-butanedioic acid, magnesium acetate, potassium acetate, and acetic anhydride were mixed in a mass ratio of 1:0.7:0.005:0.005:14, reacted at 151° C. for 4 h under a nitrogen atmosphere, heated to 222° C., kept warm for 4 h, heated to 248° C., kept warm for 4 h, evacuated for 29 min, cooled to room temperature, taken out, washed with acetone 6 times, and dried at 80° C. and a vacuum degree of 0.1 MPa for 9 h to obtain a polyester compound;

[0052] (4) The polyester compound and chloroform were mixed in a mass ratio of 1:296, and after ultrasonication at 25kHz for 44 minutes, a Span solution 32 times the mass of the polyester compound was added, wherein the mass ratio of Span 80 to chloroform in the Span solution was 1:8, and ultrasonication was continued for 44 minutes, and chitosan 1.8 times the mass of the polyester compound was added, and ultrasonication was continued for 26 minutes, and then a Tween mixed solution 2040 times the mass of the polyester compound was added, wherein the mass ratio of Tween-80, polyvinyl alcohol and deionized water in the Tween mixed solution was 1:1:100, and after stirring at 1000 rpm for 18 minutes, ultrasonication was continued for 5 hours to obtain microcapsules;

[0053] (5) Mixing microcapsules, 3-chloropropyltriethoxysilane, anhydrous ethanol, and deionized water in a mass ratio of 1:1.0:9.7:0.5, and stirring at 100 rpm for 3 hours to obtain a microcapsule solution; spraying the microcapsule solution in an amount 0.4 times the mass of the piezoelectric ceramic non-woven fabric onto the piezoelectric ceramic non-woven fabric, treating at 100° C. for 70 minutes, cooling to room temperature, and washing with anhydrous ethanol for 6 times to obtain a repaired non-woven fabric layer;

[0054] (6) The weight is 60g / m 2The polypropylene non-woven fabric is placed in a plasma device, argon and oxygen are introduced at a flow ratio of 17:3, and the pre-treated non-woven fabric is treated at 60W for 10 minutes to obtain a pre-treated non-woven fabric; the pre-treated non-woven fabric is placed in a 2-hydroxybutyric acid methyl ester solution with a mass ratio of 10 times the mass of the pre-treated non-woven fabric, and the mass ratio of 2-hydroxybutyric acid methyl ester and Tris buffer in the 2-hydroxybutyric acid methyl ester solution is 1:0.68. After soaking for 3 hours, it is taken out, washed with deionized water 7 times, and dried at 60°C and a vacuum degree of 0.1MPa for 6 hours to obtain an esterified non-woven fabric; the esterified non-woven fabric, hydrazine hydrate, anhydrous ethanol, and deionized water are mixed at a mass ratio of 1:0.8:96:6, heated at 60rpm and 60°C for 9.5 hours, then heated to 90°C, heated for 4 hours, taken out, washed with deionized water and ethyl acetate 8 times in sequence, and dried at 60°C for 10 hours to obtain a hydrazide non-woven fabric;

[0055] (7) Hydrazide non-woven fabric, 1-(dimethylamino)-2-methyl-3-pentanone, and anhydrous ethanol were mixed in a mass ratio of 1:0.8:109, reacted at 60°C for 10 hours, taken out, and washed with deionized water 7 times to obtain an acylhydrazone compound; at 45°C, the acylhydrazone compound, 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde, and cyclohexane were mixed in a mass ratio of 1:0.7:12, reacted for 14 hours, cooled to room temperature, allowed to stand for 10 hours, taken out, washed with anhydrous ethanol 10 times, and then washed with deionized water 6 times, and dried at 60°C for 10 hours to obtain an antibacterial non-woven fabric;

[0056] (8) After the super absorbent resin is heated at 120° C. until it melts, carboxyl-terminated nitrile rubber, polyamide 651, and KH-550 are added in a mass ratio of 1:5:10, and the mass ratio of the toughening agent to the super absorbent resin is 0.01:1, and the mixture is stirred evenly to obtain a water-absorbent resin solution; the water-absorbent resin solution in an amount of 0.3 times the mass of the repair non-woven fabric layer is sprayed onto the repair non-woven fabric layer, and an antibacterial non-woven fabric of the same area as the repair non-woven fabric layer is attached, and the mixture is cured at 180° C. for 5 h to obtain a medical absorbent composite material.

[0057] Comparative Example 1

[0058] The difference between Comparative Example 1 and Example 2 is that there are no steps (1) and (2), and step (5) is changed to: microcapsules, 3-chloropropyltriethoxysilane, anhydrous ethanol, and deionized water are mixed in a mass ratio of 1:0.75:9.1:0.45, and stirred at 100 rpm for 2 hours to obtain a microcapsule solution; 0.3 times the mass of the polypropylene non-woven fabric is sprayed on the polypropylene non-woven fabric, treated at 100° C. for 64 minutes, cooled to room temperature, and washed with anhydrous ethanol 5 times to obtain a repaired non-woven fabric layer. The remaining steps are the same as those in Example 2.

[0059] Comparative Example 2

[0060] The difference between Comparative Example 2 and Example 2 is that there is no step (3) to (5), and step (2) is changed to: electrospinning the spinnable sol at an applied voltage of 22 kV and a receiving distance of 22 cm, drying at 90° C. for 45 h, heating to 500° C., keeping the temperature for 35 min, heating to 700° C., keeping the temperature for 60 min, heating to 1000° C., keeping the temperature for 110 min, and obtaining a repaired non-woven fabric layer. The remaining steps are the same as those in Example 2.

[0061] Comparative Example 3

[0062] The difference between Comparative Example 3 and Example 2 is that there is no step (3), and step (4) is changed to: a super absorbent resin and chloroform are mixed at a mass ratio of 1:296, and after 25kHz ultrasound for 36 minutes, a Span solution with a mass ratio of 30 times the mass of the super absorbent resin is added, and the mass ratio of Span 80 to chloroform in the Span solution is 1:8, and after continuing ultrasound for 37 minutes, chitosan with a mass ratio of 1.3 times the mass of the super absorbent resin is added, and after continuing ultrasound for 19 minutes, a Tween mixed solution with a mass ratio of 2040 times the mass of the super absorbent resin is added, and the mass ratio of Tween-80, polyvinyl alcohol, and deionized water in the Tween mixed solution is 1:1:100, and after stirring at 1000rpm for 14 minutes, ultrasound is continued for 4.5 hours to obtain microcapsules. The remaining steps are the same as those in Example 2.

[0063] Comparative Example 4

[0064] The difference between Comparative Example 4 and Example 2 is that step (6) is changed to: 2 The polypropylene nonwoven fabric is placed in a plasma device, argon and oxygen are introduced at a flow ratio of 17:3, and the pre-treated nonwoven fabric is treated at 60W for 7 minutes to obtain a pre-treated nonwoven fabric; the pre-treated nonwoven fabric, hydrazine hydrate, anhydrous ethanol, and deionized water are mixed at a mass ratio of 1:0.7:92:4.5, heated at 60rpm and 60°C for 7.8 hours, then heated to 90°C, heated for 3 hours, taken out, washed with deionized water and ethyl acetate 7 times in sequence, and dried at 60°C for 9 hours to obtain a hydrazide nonwoven fabric. The remaining steps are the same as those in Example 2.

[0065] Comparative Example 5

[0066] The difference between Comparative Example 5 and Example 2 is that step (7) is different, and step (7) is changed to: at 45°C, hydrazide non-woven fabric, 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde, and cyclohexane are mixed in a mass ratio of 1:0.55:9, reacted for 12.5 hours, cooled to room temperature, allowed to stand for 8.5 hours, taken out, washed with anhydrous ethanol 9 times, then washed with deionized water 5 times, and dried at 60°C for 9 hours to obtain an antibacterial non-woven fabric. The remaining steps are the same as those in Example 2.

[0067] Comparative Example 6

[0068] The difference between Comparative Example 6 and Example 2 is that step (7) is different, and step (7) is changed to: hydrazide non-woven fabric, 1-(dimethylamino)-2-methyl-3-pentanone, and anhydrous ethanol are mixed in a mass ratio of 1:0.65:93, reacted at 60° C. for 8.5 hours, taken out, washed with deionized water 6 times, and dried at 60° C. for 9 hours to obtain an antibacterial non-woven fabric. The remaining steps are the same as in Example 2.

[0069] Effect example

[0070] Table 1 below shows the performance analysis results of the medical water-absorbent composite materials and antibacterial non-woven fabrics of Examples 1 to 3 and Comparative Examples 1 to 6 of the present invention.

[0071] Table 1

[0072] Wound recovery Adhesion Antibacterial rate (%) Example 1 No wound, no scar No adhesion 99.5 Example 2 No wound, no scar No adhesion 99.8 Example 3 No wound, no scar No adhesion 99.4 Comparative Example 1 Wound No adhesion 99.3 Comparative Example 2 Wound Adhesion 99.2 Comparative Example 3 Wound Adhesion 99.3 Comparative Example 4 No wound, no scar No adhesion 44.8 Comparative Example 5 No wound, no scar No adhesion 77.7 Comparative Example 6 No wound, no scar No adhesion 81.2

[0073] From the comparison of the experimental data of wound recovery and adhesion between the embodiment and the comparative example, it can be found that the present invention uses bismuth nitrate, butyl titanate, barium acetate, hydrated lead acetate, and lanthanum acetate as raw materials, and after electrospinning and gradient calcination treatment, the ceramic grains gradually grow and overlap each other to form an inorganic skeleton to obtain a piezoelectric ceramic non-woven fabric, and then hydroxyacetic acid and 2-amino-4-hydroxy-1,4-succinic acid are polymerized to form a polyester compound, which has good flexibility, prevents the microcapsule wall material from adhering to the wound, and is beneficial to promoting wound healing. With this as the wall material and chitosan as the core material, a microcapsule is obtained, which is grafted on one side of the piezoelectric ceramic non-woven fabric under the action of a cross-linking agent. When the super absorbent resin on the other side of the non-woven fabric absorbs water and swells into water The gel squeezes the microcapsules and the piezoelectric ceramic non-woven fabric, causes the wall material to rupture, releases chitosan, and generates oxygen, thereby increasing the activity of fibroblasts and promoting wound healing. From the comparison of the antibacterial rate experimental data of the embodiment and the comparative example, it can be found that after the polypropylene non-woven fabric is pretreated by plasma, it reacts with 2-hydroxybutyric acid methyl ester, hydrazine hydrate, 1-(dimethylamino)-2-methyl-3-pentanone, and 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde to form a double antibacterial group, which synergizes with each other to improve the antibacterial property of the composite material. In addition, the hydrophobic group is introduced perpendicular to the surface of the non-woven fabric to form a hydrophobic barrier layer, and at the same time, it can be tightly cross-linked with the water-absorbing resin layer to improve the antibacterial property of the composite material.

[0074] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A medical water-absorbent composite material, characterized in that: The medical water-absorbing composite material comprises a repair non-woven fabric layer, a water-absorbing resin layer and an antibacterial non-woven fabric layer.

2. The water-absorbent composite material for medical use according to claim 1, characterized in that: The repair non-woven fabric layer is prepared by the following method: bismuth nitrate pentahydrate, barium acetate, lead acetate trihydrate, lanthanum acetate, ethylene glycol monomethyl ether, acetic acid, and acetylacetone are mixed, stirred and dissolved, and then a butyl titanate solution is added, and the precursor solution A is concentrated to obtain a precursor solution A; a polyvinylpyrrolidone solution is added to the precursor solution A to obtain a spinnable sol, and after electrospinning, the sol is dried for a period of time, and then the sol is heated by gradient heating to obtain a piezoelectric ceramic non-woven fabric; microcapsules are sprayed on the piezoelectric ceramic non-woven fabric, and heat treatment is performed to obtain the repair non-woven fabric layer.

3. A medical water-absorbent composite material according to claim 2, characterized in that: The microcapsules are prepared by the following method: hydroxyacetic acid, 2-amino-4-hydroxy-1,4-succinic acid, magnesium acetate, potassium acetate and acetic anhydride are mixed and heated in a gradient manner to obtain a polyester compound; the polyester compound and chloroform are ultrasonically mixed, a Span solution is added, ultrasonication is continued, chitosan is added, ultrasonication is continued, a Tween mixture is added, high-speed stirring is performed, and ultrasonication is continued.

4. The medical water-absorbent composite material according to claim 1, characterized in that: The antibacterial non-woven fabric layer is prepared by the following method: treating a polypropylene non-woven fabric with plasma to obtain a pre-treated non-woven fabric; placing the pre-treated non-woven fabric in a 2-hydroxybutyric acid methyl ester solution, soaking it for a period of time, and then esterifying the non-woven fabric; mixing the esterified non-woven fabric, hydrazine hydrate, anhydrous ethanol, and deionized water, and performing a heating treatment to obtain a hydrazide non-woven fabric; mixing the hydrazide non-woven fabric, 1-(dimethylamino)-2-methyl-3-pentanone, and anhydrous ethanol, and performing a heat treatment to obtain an acylhydrazone compound; and mixing the acylhydrazone compound, 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde, and cyclohexane to obtain an antibacterial non-woven fabric.

5. A method for preparing a medical water-absorbent composite material, characterized in that: The method comprises the following preparation steps: (1) bismuth nitrate pentahydrate, barium acetate, lead acetate trihydrate, lanthanum acetate, ethylene glycol monomethyl ether, acetic acid, and acetylacetone are mixed in a mass ratio of 1:0.6:1.5:0.1:4.8:3.6:0.1 to 1:0.8:2.4:0.2:7.6:6.0:0.1, stirred to dissolve, and then butyl titanate solution with a mass of 2.5 to 4.0 times that of barium acetate is added, stirred evenly, and concentrated at 65° C. for 29 to 41 minutes to obtain a precursor solution A; Add 0.6-0.7 times the mass of polyvinylpyrrolidone solution to the precursor solution A, and stir evenly to obtain a spinnable sol; (2) electrospinning the spinnable sol at an applied voltage of 22 kV and a receiving distance of 22 cm, drying at 90° C. for 40 to 50 h, heating to 500° C., keeping the temperature for 30 to 40 min, heating to 700° C., keeping the temperature for 50 to 70 min, heating to 1000° C., keeping the temperature for 100 to 120 min, and obtaining a piezoelectric ceramic nonwoven fabric; (3) mixing microcapsules, 3-chloropropyltriethoxysilane, anhydrous ethanol, and deionized water in a mass ratio of 1:0.5:8.5:0.4 to 1:1.0:9.7:0.5, and stirring at 100 rpm for 1 to 3 hours to obtain a microcapsule solution; spraying the microcapsule solution in an amount of 0.2 to 0.4 times the mass of the piezoelectric ceramic non-woven fabric onto the piezoelectric ceramic non-woven fabric, treating at 100° C. for 58 to 70 minutes, cooling to room temperature, and washing with anhydrous ethanol for 4 to 6 times to obtain a repaired non-woven fabric layer; (4) After the super absorbent resin is heated at 120° C. until it melts, carboxyl-terminated nitrile rubber, polyamide 651, and KH-550 are added in a mass ratio of 1:5:10, and the mass ratio of the toughening agent to the super absorbent resin is 0.01:1, and the mixture is stirred evenly to obtain a water-absorbent resin solution; the water-absorbent resin solution in an amount of 0.1 to 0.3 times the mass of the repair non-woven fabric layer is sprayed onto the repair non-woven fabric layer, and an antibacterial non-woven fabric of the same area as the repair non-woven fabric layer is attached, and the mixture is cured at 180° C. for 3 to 5 hours to obtain a medical absorbent composite material.

6. The method for preparing a medical water-absorbent composite material according to claim 5, characterized in that: The butyl titanate solution in step (1) is a mixture of butyl titanate, anhydrous ethanol and lactic acid in a mass ratio of 1:1.2:0.2; the polyvinyl pyrrolidone solution is a mixture of polyvinyl pyrrolidone and anhydrous ethanol in a mass ratio of 1:2.

4.

7. The method for preparing a medical water-absorbent composite material according to claim 5, characterized in that: The preparation method of the microcapsules in step (3) is as follows: the polyester compound and chloroform are mixed in a mass ratio of 1:296, and after ultrasonication at 25kHz for 28 to 44 minutes, a Span solution with a mass ratio of 28 to 32 times the mass of the polyester compound is added, wherein the mass ratio of Span 80 to chloroform in the Span solution is 1:8, and after ultrasonication for 30 to 44 minutes, chitosan with a mass ratio of 0.8 to 1.8 times the mass of the polyester compound is added, and after ultrasonication for 12 to 26 minutes, a Tween mixed solution with a mass ratio of 2040 times the mass of the polyester compound is added, wherein the mass ratio of Tween-80, polyvinyl alcohol and deionized water in the Tween mixed solution is 1:1:100, and after stirring at 1000rpm for 10 to 18 minutes, ultrasonication is continued for 4 to 5 hours.

8. The method for preparing a medical water-absorbent composite material according to claim 7, characterized in that: The preparation method of the polyester compound is as follows: hydroxyacetic acid, 2-amino-4-hydroxy-1,4-butanedioic acid, magnesium acetate, potassium acetate and acetic anhydride are mixed in a mass ratio of 1:0.5:0.005:0.005:7 to 1:0.7:0.005:0.005:14, react at 151°C for 2.5 to 4 hours under a nitrogen atmosphere, heat to 222°C, keep warm for 2 to 4 hours, heat to 248°C, keep warm for 2 to 4 hours, evacuate for 15 to 29 minutes, cool to room temperature, take out, wash with acetone for 4 to 6 times, and dry at 80°C and a vacuum degree of 0.1 MPa for 7.5 to 9 hours.

9. The method for preparing a medical water-absorbent composite material according to claim 5, characterized in that: The preparation method of the bacterial nonwoven fabric in step (4) is: a. Place the pretreated nonwoven fabric in a 2-hydroxybutyric acid methyl ester solution with a mass of 5 to 10 times that of the pretreated nonwoven fabric, wherein the mass ratio of 2-hydroxybutyric acid methyl ester to Tris buffer in the 2-hydroxybutyric acid methyl ester solution is 1:0.68, soak for 1 to 3 hours, take out, wash with deionized water for 5 to 7 times, and dry at 60°C and a vacuum degree of 0.1 MPa for 4 to 6 hours to obtain an esterified nonwoven fabric; mix the esterified nonwoven fabric, hydrazine hydrate, anhydrous ethanol, and deionized water in a mass ratio of 1:0.6:88:3 to 1:0.8:96:6, heat at 60 rpm and 60°C for 6 to 9.5 hours, heat to 90°C, heat for 2 to 4 hours, take out, wash with deionized water and ethyl acetate for 6 to 8 times in sequence, and dry at 60°C for 8 to 10 hours to obtain a hydrazide nonwoven fabric; b. Mix hydrazide non-woven fabric, 1-(dimethylamino)-2-methyl-3-pentanone and anhydrous ethanol in a mass ratio of 1:0.5:77 to 1:0.8:109, react at 60°C for 7 to 10 hours, take out, and wash with deionized water for 5 to 7 times to obtain an acylhydrazone compound; at 45°C, mix the acylhydrazone compound, 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde and cyclohexane in a mass ratio of 1:0.4:6 to 1:0.7:12, react for 11 to 14 hours, cool to room temperature, stand for 7 to 10 hours, take out, wash with anhydrous ethanol for 8 to 10 times, then wash with deionized water for 4 to 6 times, and dry at 60°C for 8 to 10 hours to obtain an antibacterial non-woven fabric.

10. The method for preparing a medical water-absorbent composite material according to claim 9, characterized in that: The preparation method of the pre-treated non-woven fabric in step a is as follows: 2 The polypropylene nonwoven fabric was placed in a plasma device, and argon and oxygen were introduced at a flow ratio of 17:3, and treated at 60W for 4 to 10 minutes.