阅读说明：本技术 一种强拉力医用无纺布 (Medical non-woven fabric with high tensile force ) 是由 承逸 于 2021-09-06 设计创作，主要内容包括：本发明涉及一种强拉力医用无纺布,属于医用无纺布制备技术领域,包括以下重量份原料：PP全新料80-100份、光催化纤维10-15份、芳纶纤维30-50份、改性碳纤维28-30份、增韧剂1-5份、相容剂2-4份、抗氧剂1-3份、润滑剂1-2份；其中改性碳纤维由酸化碳纤维和改性剂在4-二甲氨基吡啶和N,N’-二环己基碳二亚胺作用下发生酰胺反应得到,将其加入无纺布材料中,能够有效增加无纺布的抗拉性能、杀菌作用、疏水性和耐溶剂型；克服现有技术中抗菌剂容易溶出的问题,因此,本发明制备的无纺布在医用领域具有很高的利用价值。(The invention relates to a high-tensile medical non-woven fabric, which belongs to the technical field of medical non-woven fabric preparation and comprises the following raw materials in parts by weight: 80-100 parts of PP complete and new material, 10-15 parts of photocatalytic fiber, 30-50 parts of aramid fiber, 28-30 parts of modified carbon fiber, 1-5 parts of toughening agent, 2-4 parts of compatilizer, 1-3 parts of antioxidant and 1-2 parts of lubricant; the modified carbon fiber is obtained by the amide reaction of acidified carbon fiber and a modifier under the action of 4-dimethylamino pyridine and N, N' -dicyclohexyl carbodiimide, and the modified carbon fiber is added into a non-woven fabric material, so that the tensile property, the bactericidal effect, the hydrophobicity and the solvent resistance of the non-woven fabric can be effectively improved; the problem that the antibacterial agent is easy to dissolve in the prior art is solved, so that the non-woven fabric prepared by the method has high utilization value in the medical field.)

1. A high-tensile-force medical non-woven fabric is characterized by comprising the following raw materials: PP (polypropylene) complete material, photocatalytic fiber, aramid fiber, modified carbon fiber, toughening agent, compatilizer, antioxidant and lubricant;

the modified carbon fiber is prepared by the following steps:

mixing acidified carbon fibers, triethylamine and tetrahydrofuran, adding a modifier at 0 ℃, then adding 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide, heating to 25 ℃, reacting for 3 hours, concentrating the reaction liquid to 1/3 of the original volume, extracting the concentrated liquid with ethyl acetate, washing an organic phase with a sodium bicarbonate solution, and distilling under reduced pressure to obtain the modified carbon fibers.

2. A high-tensile medical non-woven fabric according to claim 1, which is characterized by comprising the following raw materials in parts by weight:

80-100 parts of PP complete and new material, 10-15 parts of photocatalytic fiber, 30-50 parts of aramid fiber, 28-30 parts of modified carbon fiber, 1-5 parts of toughening agent, 2-4 parts of compatilizer, 1-3 parts of antioxidant and 1-2 parts of lubricant.

3. A high tensile force medical nonwoven fabric according to claim 1, wherein the acidified carbon fibers are prepared by the steps of:

and (3) placing the pretreated carbon fiber in a concentrated nitric acid solution, performing ultrasonic treatment for 30min, heating to 45 ℃, stirring for reaction for 3h, washing, performing suction filtration, and drying to obtain the acidified carbon fiber.

4. A high tensile force medical non-woven fabric according to claim 3, wherein the pre-treated carbon fiber is prepared by the steps of:

cutting the chopped carbon fibers to 0.5-1cm, soaking in an acetone solution at normal temperature for 20h, carrying out ultrasonic treatment for 3h, taking out, washing and drying to obtain the pretreated carbon fibers.

5. A high tensile medical nonwoven fabric according to claim 1, wherein the modifier is prepared by the following steps:

step A1, under the protection of nitrogen, mixing perfluorooctyl iodide, caproleic acid and toluene, heating to 80 ℃, adding AIBN with equal quantity for four times within 6 hours, performing reflux reaction for 4-6 hours at an interval of 1.5 hours each time, and performing reduced pressure distillation to obtain an intermediate 3;

step A2, mixing the intermediate 3, anhydrous toluene, tributyl tin oxide and AIBN, controlling the reaction temperature at 80 ℃, stirring for 24 hours, washing, filtering and drying to obtain an intermediate 4;

and step A3, mixing the intermediate 4, the pyridine quaternary ammonium salt compound and toluene, stirring, adding p-toluenesulfonic acid, performing reflux reaction for 2-3h, washing, and performing reduced pressure distillation to obtain the modifier.

6. A high-tensile medical nonwoven fabric as claimed in claim 5, wherein the quaternary ammonium salt compound is prepared by the following steps:

step B1, mixing 5, 5-dimethylhydantoin and acetone, adding potassium carbonate, carrying out reflux reaction for 30min, adding 1, 4-dibromobutane, carrying out reflux reaction for 4-5h, filtering while hot to remove inorganic salts, collecting filtrate, carrying out reduced pressure distillation, and separating and purifying a distillation product by a chromatographic column to obtain an intermediate 1;

and step B2, mixing the 3, 5-pyridinedimethanol and the ethanol solution, heating to 40 ℃, adding the ethanol solution of the intermediate 1, heating to 45 ℃, reacting for 7-8h under the condition of heat preservation, distilling under reduced pressure, washing, filtering, and evaporating the filtrate to dryness under reduced pressure to obtain the pyridine quaternary ammonium salt compound.

7. The medical nonwoven fabric with high tensile force according to claim 6, wherein the ethanol solution of the intermediate 1 in the step B2 is prepared from the intermediate 1 and ethanol according to a ratio of 1 mmol: 10mL of the above-mentioned components were mixed.

8. A medical non-woven fabric with high tensile force according to claim 1, wherein the toughening agent is one or two of ACR resin and MBS resin which are mixed according to any proportion.

9. A high tensile medical nonwoven fabric according to claim 1, wherein the preparation method of the nonwoven fabric comprises the following steps:

firstly, mixing, melting, spinning and drafting raw materials to obtain composite fibers;

and secondly, stacking and paving the composite fibers into a fiber web, and shaping the fiber web by a press roller to obtain the medical non-woven fabric with strong tension.

10. A high tensile medical nonwoven fabric according to claim 9, wherein the roll pressure is 5kg and the roll linear speed is 200 m/min.

Technical Field

The invention belongs to the technical field of medical non-woven fabric preparation, and particularly relates to a high-tensile medical non-woven fabric.

Background

The medical non-woven fabric is mainly made of polyester, polyamide, polytetrafluoroethylene, PP (polypropylene) complete and new materials, carbon fiber and glass fiber, and the prepared non-woven fabric products comprise disposable masks, protective clothing, surgical gowns, isolation gowns and medical coating materials, but the conventional medical non-woven fabric often has the problems of poor toughness and non-durable antibacterial property.

Chinese patent CN112111851A discloses an antibacterial medical non-woven fabric and a preparation process thereof, which belong to the technical field of non-woven fabrics and comprise the following components in parts by mass: 90-110 parts of PP full-new material fiber, 80-100 parts of polyester fiber, 1-3 parts of organic montmorillonite, 20-25 parts of activated carbon fiber, 1-3 parts of crystal wax, 4-10 parts of antibacterial agent, 1-3 parts of antistatic agent and 0.5-2 parts of antioxidant, the invention adds the ethoxylation aliphatic alkylamine in the non-woven fabric raw material as the antibacterial agent to effectively sterilize, the ethoxylation aliphatic alkylamine can effectively enhance the sterilizing capability with the crystal wax and the organic montmorillonite through the high temperature reaction, however, the antibacterial agent in the invention is easy to dissolve out and separate from the non-woven fabric, so that the non-woven fabric loses antibacterial performance, the preparation process of the non-woven fabric is complex, after the fiber is loosened and melted and extruded, the reinforcing method has higher production cost and does not use mass production.

Disclosure of Invention

The invention aims to provide a medical non-woven fabric with high tensile force, which is used for solving the technical problems mentioned in the background technology.

The purpose of the invention can be realized by the following technical scheme:

a high-tensile-force medical non-woven fabric comprises the following raw materials in parts by weight: 80-100 parts of PP complete and new material, 10-15 parts of photocatalytic fiber, 30-50 parts of aramid fiber, 28-30 parts of modified carbon fiber, 1-5 parts of toughening agent, 2-4 parts of compatilizer, 1-3 parts of antioxidant and 1-2 parts of lubricant;

the medical non-woven fabric with high tensile force is prepared by the following steps:

firstly, adding the raw materials into a mixer, mixing at the rotating speed of 100-200r/min for 20min, transferring the mixture to a screw extruder for melting, outputting the molten mixture through a spinning hole, and drafting to obtain composite fibers;

and secondly, stacking and paving the composite fibers into a fiber web, and shaping the fiber web by a press roller to obtain the medical non-woven fabric with strong tension.

Further, the melting temperature was 240 ℃,

further, the press roll pressure was 5kg, and the linear speed of the press roll was 200 m/min.

Further, the modified carbon fiber is prepared by the following steps:

step 1, adding 5, 5-dimethylhydantoin and acetone into a three-neck flask, adding potassium carbonate for reflux reaction for 30min, adding 1, 4-dibromobutane, continuing reflux reaction for 4-5h, filtering to remove inorganic salts while the solution is hot after the reaction is finished, collecting filtrate, removing the solvent by reduced pressure distillation, separating and purifying a distillation product by a chromatographic column, and performing separation and purification by using a volume ratio of ethyl acetate to petroleum ether of 2: 5 as eluent, collecting organic phase, and distilling under reduced pressure to obtain intermediate 1;

wherein the dosage ratio of the 5, 5-dimethylhydantoin to the acetone to the potassium carbonate to the 1, 4-dibromobutane is 1.28 g: 100mL of: 4.12-5.35 g: 8.12-8.78 g;

under alkaline conditions, 5-dimethylhydantoin and 1, 4-dibromobutane are subjected to HCl elimination reaction to obtain an intermediate 1, wherein the reaction process is as follows:

step 2, adding 3, 5-pyridinedimethanol and an ethanol solution with the mass fraction of 40% into a three-neck flask, stirring and heating to 40 ℃, adding the ethanol solution of the intermediate 1, heating to 45 ℃, keeping the temperature and reacting for 7-8h, after the reaction is finished, carrying out reduced pressure distillation to remove ethanol, adding deionized water, washing, filtering, and evaporating the filtrate to dryness under reduced pressure to obtain an intermediate 2, namely a pyridine quaternary ammonium salt compound;

wherein the dosage ratio of the 3, 5-pyridine dimethanol to the ethanol solution of the intermediate 1 is 1 mmol: 80-100 mL: 10mL, wherein the ethanol solution of intermediate 1 was prepared from intermediate 1 and absolute ethanol according to a1 mmol: 10mL of the mixture is mixed;

the 3, 5-pyridinedimethanol and the intermediate 1 are chemically reacted to obtain an intermediate 2, namely a pyridine quaternary ammonium salt compound, and the reaction process is as follows:

step 3, under the protection of nitrogen, adding perfluorooctyl iodide, caproleic acid and toluene into a three-neck flask, heating to 80 ℃, adding AIBN with equal quantity for four times within 6 hours, wherein each time interval is 1.5 hours, then carrying out reflux reaction for 4-6 hours, and after the reaction is finished, carrying out reduced pressure distillation to remove the toluene to obtain an intermediate 3;

wherein the dosage ratio of the perfluorooctyl iodine, the caproleic acid, the toluene and the AIBN is 0.05 mol: 0.05 mol: 78.2-83.4 mL: 100 mg;

the chemical reaction of perfluorooctyl iodine and caproleic acid to obtain intermediate 3 includes the following steps:

step 4, adding the intermediate 3, anhydrous toluene, tributyl tin oxide and AIBN into a three-neck flask, controlling the reaction temperature to be 80 ℃, stirring and reacting for 24 hours under the condition of the rotating speed of 100-;

wherein the dosage ratio of the intermediate 3, the anhydrous toluene, the tributyl tin oxide and the AIBN is 0.05 mol: 100-120 mL: 21.2-23.4 g: 0.41-0.66 g;

enabling the intermediate 3 to perform chemical reaction under the action of tributyl tin oxide and AIBN to obtain an intermediate 4, wherein the chemical reaction process is as follows:

step 5, adding the intermediate 4, the intermediate 2 and toluene into a reaction kettle, stirring and adding p-toluenesulfonic acid under the condition that the rotation speed is 100-200r/min, heating to reflux reaction for 2-3h, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the concentration of 0.1mol/L for washing, standing for layering, and carrying out vacuum distillation on the organic phase to obtain a modifier;

wherein the dosage ratio of the intermediate 4 to the intermediate 2 to the toluene is 0.1 mol: 0.05 mol: 64.2-81.7mL, wherein the dosage of the p-toluenesulfonic acid is 2-4% of the total mass of the intermediate 4 and the intermediate 2;

under the catalytic action of p-toluenesulfonic acid, the intermediate 4 and the intermediate 2 are subjected to esterification reaction to obtain a modifier, wherein the reaction process is as follows:

step 6, cutting the chopped carbon fibers to 0.5-1cm, soaking the chopped carbon fibers in an acetone solution at normal temperature for 20 hours, carrying out ultrasonic treatment for 3 hours, taking out the chopped carbon fibers, washing the chopped carbon fibers with deionized water for 3-5 times, and drying the chopped carbon fibers at 50 ℃ to constant weight to obtain pretreated carbon fibers;

step 7, placing the pretreated carbon fibers in a concentrated nitric acid solution, performing ultrasonic treatment for 30min, heating to 45 ℃, stirring for reaction for 3h, then adding deionized water for washing, performing suction filtration, washing a filter cake with the deionized water until a washing solution is neutral, and drying at 80 ℃ to constant weight to obtain acidified carbon fibers; wherein the dosage ratio of the pretreated carbon fiber to the concentrated nitric acid solution is 3.1-3.5 g: 30-35 mL; 65% of concentrated nitric acid solution by mass;

step 8, magnetically stirring the acidified carbon fibers, triethylamine and tetrahydrofuran in a three-neck flask, adding a modifier at 0 ℃, then adding 4-dimethylaminopyridine and N, N '-dicyclohexylcarbodiimide, heating to 25 ℃, reacting for 3 hours, concentrating the reaction solution to 1/3 of the original volume, extracting and shaking the concentrated solution with ethyl acetate, putting the concentrated solution into a refrigerator at-1 ℃ for 12 hours, washing an organic phase with a sodium bicarbonate solution with the mass fraction of 5% for 3-5 times, and distilling under reduced pressure to obtain the modified carbon fibers, wherein the dosage ratio of the acidified carbon fibers, the triethylamine, the tetrahydrofuran, the modifier, the 4-dimethylaminopyridine and the N, N' -dicyclohexylcarbodiimide is 5.4-5.8 g: 1.1-1.5 g: 100-150 mL: 1.5-1.8 g: 0.48-0.52 g: 0.71-0.84 g.

Furthermore, the toughening agent is formed by mixing one or two of ACR resin and MBS resin according to any proportion.

Further, the compatilizer is one or two of styrene-maleic anhydride copolymer and polyformaldehyde which are mixed according to any proportion.

Furthermore, the antioxidant is one or two of antioxidant 168 and antioxidant 1010 which are mixed according to any proportion.

Further, the lubricant is formed by mixing one or more of stearic acid, low-carbon alcohol, fatty acid and polyether according to any proportion.

The invention has the beneficial effects that:

according to the invention, a medical non-woven fabric is obtained by taking a PP (polypropylene) brand-new material, photocatalytic fibers, aramid fibers, modified carbon fibers and an auxiliary agent as raw materials through melting, spinning, laying into a net and spunlacing for reinforcement, and has excellent antibacterial property and mechanical property and high utilization value in the medical field;

the photocatalytic fiber is obtained by perfectly combining nano titanium dioxide and a high polymer material by adopting a modern composite technology and then carrying out melt spinning, and the most distinctive feature of the fiber is that each fiber has a honeycomb microporous structure penetrating from inside to outside, the specific surface area is extremely large, and the fiber has the effects of self-cleaning, sterilization, deodorization and mildew prevention;

the preparation method is mainly characterized by firstly preparing a pyridine quaternary ammonium salt compound intermediate 2 through a chemical reaction, further synthesizing an intermediate 4 containing terminal amino, carboxyl and F-C long chains through a chemical means, carrying out an esterification reaction on the intermediate 2 and the intermediate 4 to obtain a modifier, then cleaning carbon fibers in acetone to remove impurities, acidifying in concentrated nitric acid to obtain acidified carbon fibers with carboxyl on the surfaces, and then utilizing an amide reaction between the carboxyl and the amino to graft the modifier on the surfaces of the carbon fibers through chemical bonds to obtain modified carbon fibers, so that the modifier is not easy to dissolve out and fall off; according to the invention, the carbon fiber is modified, not only based on the characteristics of high temperature resistance, friction resistance, electric conduction, heat conduction and corrosion resistance of the carbon fiber, but also based on high strength and high modulus of the carbon fiber, the carbon fiber is added into a non-woven fabric material, so that the tensile property of the non-woven fabric can be effectively increased, the quaternary pyridinium salt structure has a very strong bactericidal effect and can act on a lipid bilayer of a cell membrane, the positive charge of the quaternary pyridinium salt acts with the head group of acidic phosphate in the membrane, and a hydrophobic hydrocarbon group is inserted into the middle of a hydrophobic membrane, so that the soaking capacity is reduced, cytosol such as potassium ions and the like is leaked out, cells die, the C-F bond length is short, the bond energy is high, the free energy of the surface of a solvent-based substance containing a large number of C-F bonds is low, and the carbon fiber has high hydrophobicity and solvent resistance;

the modified carbon fiber contains a plurality of N-H bonds, and after hypochlorite rinsing, the N-H bonds are oxidized into N-Cl bonds to form a haloamine bactericide, so that a new bactericidal function is obtained;

the cloth is shaped by using the novel material and the pressing roller with square points, so that the transverse and longitudinal strengths of the cloth are consistent, and the non-woven fabric has high tensile force;

in conclusion, the non-woven fabric prepared by the invention has lasting antibacterial performance, better mechanical property and self-cleaning performance.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

This example prepares a modified carbon fiber by the following steps:

step 1, adding 1.28g of 5, 5-dimethylhydantoin and 100mL of acetone into a three-neck flask, adding 4.12g of potassium carbonate for reflux reaction for 30min, adding 8.12g of 1, 4-dibromobutane, continuing reflux reaction for 4h, filtering to remove inorganic salts when the reaction is hot after the reaction is finished, collecting filtrate, removing the solvent by reduced pressure distillation, separating and purifying a distillation product by a chromatographic column, wherein the volume ratio of ethyl acetate to petroleum ether is 2: 5 as eluent, collecting organic phase, and distilling under reduced pressure to obtain intermediate 1;

step 2, adding 1mmol of 3, 5-pyridinedimethanol and 80mL of ethanol solution with mass fraction of 40% into a three-neck flask, stirring and heating to 40 ℃, adding 10mL of ethanol solution of the intermediate 1, heating to 45 ℃, preserving heat and reacting for 7 hours, after the reaction is finished, removing ethanol through reduced pressure distillation, adding deionized water for washing, filtering, and evaporating water from the filtrate under reduced pressure to obtain an intermediate 2, wherein the ethanol solution of the intermediate 1 is prepared from the intermediate 1 and absolute ethanol according to the mass fraction of 1 mmol: 10mL of the mixture is mixed;

step 3, under the protection of nitrogen, adding 0.05mol of perfluorooctyl iodide, 0.05mol of aminocaproic acid and 78.2mL of toluene into a three-neck flask, heating to 80 ℃, adding 100mg of AIBN equivalently for four times within 6h at an interval of 1.5h every time, then carrying out reflux reaction for 4h, and after the reaction is finished, carrying out reduced pressure distillation to remove the toluene to obtain an intermediate 3;

step 4, adding 0.05mol of the intermediate 3, 100mL of anhydrous toluene, 21.2g of tributyltin oxide and 0.41g of AIBN into a three-neck flask, controlling the reaction temperature to be 80 ℃, stirring and reacting for 24 hours at the rotating speed of 100r/min, cooling to room temperature after the reaction is finished, washing with toluene, filtering, and drying to obtain an intermediate 4;

step 5, adding 0.1mol of the intermediate 4, 0.05mol of the intermediate 2 and 64.2mL of toluene into a reaction kettle, stirring and adding p-toluenesulfonic acid under the condition that the rotating speed is 100r/min, heating to reflux for reaction for 2 hours, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the concentration of 0.1mol/L for washing, standing for layering, and carrying out reduced pressure distillation on an organic phase to obtain a modifier, wherein the dosage of the p-toluenesulfonic acid is 2% of the total mass of the intermediate 4 and the intermediate 2;

step 6, cutting the chopped carbon fibers to 0.5cm, soaking the chopped carbon fibers in an acetone solution at normal temperature for 20 hours, carrying out ultrasonic treatment for 3 hours, taking out the carbon fibers, washing the carbon fibers for 3 times by using deionized water, and drying the carbon fibers at 50 ℃ to constant weight to obtain pretreated carbon fibers;

step 7, placing 3.1g of pretreated carbon fibers in 30mL of concentrated nitric acid solution, performing ultrasonic treatment for 30min, heating to 45 ℃, stirring for reaction for 3h, then adding deionized water for washing, performing suction filtration, washing a filter cake with deionized water until a washing solution is neutral, and drying at 80 ℃ to constant weight to obtain acidified carbon fibers;

and 8, magnetically stirring 5.4g of acidified carbon fiber, 1.1g of triethylamine and 100mL of tetrahydrofuran in a three-neck flask, adding 1.5g of a modifier at 0 ℃, then adding 0.48g of 4-dimethylaminopyridine and 0.71g N, N' -dicyclohexylcarbodiimide, heating to 25 ℃, reacting, concentrating the reaction solution to the original volume of 1/3, extracting and shaking the concentrated solution with ethyl acetate, placing the concentrated solution into a refrigerator at-1 ℃ for 12 hours, washing the organic phase with a sodium bicarbonate solution with the mass fraction of 5% for 3 times, and distilling under reduced pressure to obtain the modified carbon fiber.

Example 2

This example prepares a modified carbon fiber by the following steps:

step 1, adding 1.28g of 5, 5-dimethylhydantoin and 100mL of acetone into a three-neck flask, adding 4.82g of potassium carbonate for reflux reaction for 30min, adding 8.23g of 1, 4-dibromobutane, continuing reflux reaction for 4.5h, filtering to remove inorganic salts when the reaction is finished, collecting filtrate, distilling under reduced pressure to remove the solvent, separating and purifying a distillation product by a chromatographic column, and performing separation and purification by using a volume ratio of ethyl acetate to petroleum ether of 2: 5 as eluent, collecting organic phase, and distilling under reduced pressure to obtain intermediate 1;

step 2, adding 1mmol of 3, 5-pyridinedimethanol and 90mL of ethanol solution with mass fraction of 40% into a three-neck flask, stirring and heating to 40 ℃, adding 10mL of ethanol solution of the intermediate 1, heating to 45 ℃, preserving heat and reacting for 7.5h, after the reaction is finished, removing ethanol through reduced pressure distillation, adding deionized water for washing, filtering, and evaporating moisture from the filtrate through reduced pressure to obtain an intermediate 2, wherein the ethanol solution of the intermediate 1 is prepared from the intermediate 1 and absolute ethanol according to the mass fraction of 1 mmol: 10mL of the mixture is mixed;

step 3, under the protection of nitrogen, adding 0.05mol of perfluorooctyl iodide, 0.05mol of aminocaproic acid and 79.6mL of toluene into a three-neck flask, heating to 80 ℃, adding 100mg of AIBN equivalently for four times within 6h at intervals of 1.5h every time, then carrying out reflux reaction for 5h, and after the reaction is finished, carrying out reduced pressure distillation to remove the toluene to obtain an intermediate 3;

step 4, adding 0.05mol of the intermediate 3, 110mL of anhydrous toluene, 22.6g of tributyltin oxide and 0.52g of AIBN into a three-neck flask, controlling the reaction temperature to be 80 ℃, stirring and reacting for 24 hours at the rotating speed of 150r/min, cooling to room temperature after the reaction is finished, washing with toluene, filtering, and drying to obtain an intermediate 4;

step 5, adding 0.1mol of the intermediate 4, 0.05mol of the intermediate 2 and 69.6mL of toluene into a reaction kettle, stirring and adding p-toluenesulfonic acid under the condition that the rotating speed is 150r/min, heating to reflux for reaction for 2.5h, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the concentration of 0.1mol/L for washing, standing for layering, and carrying out reduced pressure distillation on an organic phase to obtain a modifier, wherein the dosage of the p-toluenesulfonic acid is 3% of the total mass of the intermediate 4 and the intermediate 2;

step 6, cutting the chopped carbon fibers to 0.8cm, soaking the chopped carbon fibers in an acetone solution at normal temperature for 20 hours, carrying out ultrasonic treatment for 3 hours, taking out the chopped carbon fibers, washing the chopped carbon fibers with deionized water for 4 times, and drying the chopped carbon fibers at 50 ℃ to constant weight to obtain pretreated carbon fibers;

step 7, placing the pretreated carbon fibers in a concentrated nitric acid solution, performing ultrasonic treatment for 30min, heating to 45 ℃, stirring for reaction for 3h, then adding deionized water for washing, performing suction filtration, washing a filter cake with the deionized water until a washing solution is neutral, and drying at 80 ℃ to constant weight to obtain acidified carbon fibers; wherein the dosage ratio of the treated carbon fiber to the concentrated nitric acid solution is 3.3 g: 34 mL;

and step 8, magnetically stirring 5.6g of acidified carbon fiber, 1.4g of triethylamine and 120mL of tetrahydrofuran in a three-neck flask, adding 1.7g of modifier at 0 ℃, then adding 0.49g of 4-dimethylaminopyridine and 0.82g N, N' -dicyclohexylcarbodiimide, heating to 25 ℃, reacting for 3 hours, concentrating the reaction liquid to the original volume of 1/3, extracting and shaking the concentrated liquid with ethyl acetate, placing the concentrated liquid in a refrigerator at-1 ℃ for 12 hours, washing the organic phase with a sodium bicarbonate solution with the mass fraction of 5% for 4 times, and distilling under reduced pressure to obtain the modified carbon fiber.

Example 3

This example prepares a modified carbon fiber by the following steps:

step 1, adding 1.28g of 5, 5-dimethylhydantoin and 100mL of acetone into a three-neck flask, adding 5.35g of potassium carbonate for reflux reaction for 30min, adding 8.78g of 1, 4-dibromobutane, continuing reflux reaction for 5h, filtering to remove inorganic salts when the reaction is hot after the reaction is finished, collecting filtrate, removing the solvent by reduced pressure distillation, separating and purifying a distillation product by a chromatographic column, wherein the volume ratio of ethyl acetate to petroleum ether is 2: 5 as eluent, collecting organic phase, and distilling under reduced pressure to obtain intermediate 1;

step 2, adding 1mmol of 3, 5-pyridinedimethanol and 100mL of ethanol solution with mass fraction of 40% into a three-neck flask, stirring and heating to 40 ℃, adding 10mL of ethanol solution of the intermediate 1, heating to 45 ℃, preserving heat and reacting for 8 hours, after the reaction is finished, removing ethanol through reduced pressure distillation, adding deionized water for washing, filtering, and evaporating water from the filtrate under reduced pressure to obtain an intermediate 2, wherein the ethanol solution of the intermediate 1 is prepared from the intermediate 1 and absolute ethanol according to the mass fraction of 1 mmol: 10mL of the mixture is mixed;

step 3, under the protection of nitrogen, adding 0.05mol of perfluorooctyl iodide, 0.05mol of aminocaproic acid and 83.4mL of toluene into a three-neck flask, heating to 80 ℃, adding 100mg of AIBN equivalently for four times within 6h at an interval of 1.5h every time, then carrying out reflux reaction for 6h, and after the reaction is finished, carrying out reduced pressure distillation to remove the toluene to obtain an intermediate 3;

step 4, adding 0.05mol of the intermediate 3, 120mL of anhydrous toluene, 23.4g of tributyltin oxide and 0.66g of AIBN into a three-neck flask, controlling the reaction temperature to be 80 ℃, stirring and reacting for 24 hours at the rotating speed of 200r/min, cooling to room temperature after the reaction is finished, washing with toluene, filtering, and drying to obtain an intermediate 4;

step 5, adding 0.1mol of the intermediate 4, 0.05mol of the intermediate 2 and 81.7mL of toluene into a reaction kettle, stirring and adding p-toluenesulfonic acid under the condition of the rotation speed of 200r/min, heating to reflux for reaction for 3h, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the concentration of 0.1mol/L for washing, standing for layering, and carrying out reduced pressure distillation on an organic phase to obtain a modifier, wherein the dosage of the p-toluenesulfonic acid is 4% of the total mass of the intermediate 4 and the intermediate 2;

step 6, cutting the chopped carbon fibers to 1cm, soaking the chopped carbon fibers in an acetone solution at normal temperature for 20 hours, carrying out ultrasonic treatment for 3 hours, taking out the chopped carbon fibers, washing the chopped carbon fibers with deionized water for 5 times, and drying the chopped carbon fibers at 50 ℃ to constant weight to obtain pretreated carbon fibers;

step 7, placing the pretreated carbon fibers in a concentrated nitric acid solution, performing ultrasonic treatment for 30min, heating to 45 ℃, stirring for reaction for 3h, then adding deionized water for washing, performing suction filtration, washing a filter cake with the deionized water until a washing solution is neutral, and drying at 80 ℃ to constant weight to obtain acidified carbon fibers; wherein the dosage ratio of the treated carbon fiber to the concentrated nitric acid solution is 3.5 g: 35 mL;

and step 8, magnetically stirring 5.8g of acidified carbon fiber, 1.5g of triethylamine and 150mL of tetrahydrofuran in a three-neck flask, adding 1.8g of modifier at 0 ℃, then adding 0.52g of 4-dimethylaminopyridine and 0.84g N, N' -dicyclohexylcarbodiimide, heating to 25 ℃, reacting for 3 hours, concentrating the reaction liquid to the original volume of 1/3, extracting and shaking the concentrated liquid with ethyl acetate, placing the concentrated liquid in a refrigerator at-1 ℃ for 12 hours, washing the organic phase with a sodium bicarbonate solution with the mass fraction of 5% for 5 times, and distilling under reduced pressure to obtain the modified carbon fiber.

Example 4

A high-tensile-force medical non-woven fabric comprises the following raw materials in parts by weight: 80 parts of PP complete and new material, 10 parts of photocatalytic fiber, 30 parts of aramid fiber, 28 parts of modified carbon fiber in example 1, 1 part of toughening agent, 2 parts of compatilizer, 1 part of antioxidant and 1 part of lubricant;

the medical non-woven fabric with high tensile force is prepared by the following steps:

firstly, adding the raw materials into a mixer, mixing at the rotating speed of 100r/min for 20min, melting at the temperature of 185 ℃, outputting through a spinning hole after melting, and drafting to obtain composite fibers;

and secondly, stacking and paving the composite fibers into a fiber web, and shaping the fiber web by a press roller to obtain the medical non-woven fabric with strong tension.

Wherein the melting temperature is 240 ℃, the pressure of a press roll is 5kg, and the linear speed of the press roll is 200 m/min.

Wherein, the toughening agent is ACR resin, the compatilizer is styrene-maleic anhydride copolymer, the antioxidant is antioxidant 168, and the lubricant is stearic acid.

Example 5

A high-tensile-force medical non-woven fabric comprises the following raw materials in parts by weight: 90 parts of PP (polypropylene) new material, 12 parts of photocatalytic fiber, 40 parts of aramid fiber, 29 parts of modified carbon fiber of example 2, 2 parts of toughening agent, 3 parts of compatilizer, 2 parts of antioxidant and 1.5 parts of lubricant;

the medical non-woven fabric with high tensile force is prepared by the following steps:

firstly, adding the raw materials into a mixer, mixing at the rotating speed of 150r/min for 20min, melting at the temperature of 195 ℃, outputting through a spinning hole after melting, and drafting to obtain composite fibers;

and secondly, stacking and paving the composite fibers into a fiber web, and shaping the fiber web by a press roller to obtain the medical non-woven fabric with strong tension.

Wherein the melting temperature is 240 ℃, the pressure of a press roll is 5kg, and the linear speed of the press roll is 200 m/min.

Wherein, the toughening agent is ACR resin, the compatilizer is styrene-maleic anhydride copolymer, the antioxidant is antioxidant 168, and the lubricant is stearic acid.

Example 6

A high-tensile-force medical non-woven fabric comprises the following raw materials in parts by weight: 100 parts of PP (polypropylene) new material, 15 parts of photocatalytic fiber, 50 parts of aramid fiber, 30 parts of modified carbon fiber in example 3, 5 parts of toughening agent, 4 parts of compatilizer, 3 parts of antioxidant and 2 parts of lubricant;

the medical non-woven fabric with high tensile force is prepared by the following steps:

firstly, adding the raw materials into a mixer, mixing at the rotating speed of 200r/min for 20min, melting at the temperature of 210 ℃, outputting through a spinning hole after melting, and drafting to obtain composite fibers;

and secondly, stacking and paving the composite fibers into a fiber web, and shaping the fiber web by a press roller to obtain the medical non-woven fabric with strong tension.

Wherein the melting temperature is 240 ℃, the pressure of a press roll is 5kg, and the linear speed of the press roll is 200 m/min.

Wherein, the toughening agent is ACR resin, the compatilizer is styrene-maleic anhydride copolymer, the antioxidant is antioxidant 168, and the lubricant is stearic acid.

Comparative example 1

The modified carbon fiber in example 4 was removed, and the remaining raw materials and preparation process were unchanged.

Comparative example 2

The modified carbon fiber of example 5 was replaced with a chopped carbon fiber sold by Shanghai Dynasty composite science and technology Co., Ltd, and the rest of the raw materials and the preparation process were not changed.

Comparative example 3

The comparative example is a medical nonwoven fabric sold by Baojie packaging company Limited in Anqing.

The nonwoven fabrics of examples 4 to 6 and comparative examples 1 to 3 were subjected to the following performance tests:

and (3) testing mechanical properties: the tensile property test (breaking strength) of the fabric is carried out by adopting the national standard GB/T3923.1-1997, and the tensile breaking test of the fabric mainly adopts unidirectional stress stretching, namely, the transverse strength and the longitudinal strength of a fabric test strip are tested. The size of the sample is 250 multiplied by 50mm, and the tensile force of the instrument is rated as 500N;

contact angle test: testing the size of the static contact angle by adopting a static contact angle measuring instrument;

and (3) testing antibacterial performance: according to GB/T209443-2008, evaluation of antibacterial performance of textiles part 3: the test is carried out by the oscillation method, and the test strain is escherichia coli;

performance durability: after the nonwoven fabric is washed for 50 times, the antibacterial performance and the contact angle are tested according to the method.

The test results are shown in the following table:

as can be seen from the table above, the nonwoven fabrics of examples 4-6 are excellent in antibacterial property, tensile property, hydrophobicity, and performance in the test process of comparative examples 1-3, and still have high antibacterial property and hydrophobicity after being washed for 50 times, so that the nonwoven fabrics prepared by the invention can have great application value in the medical field.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.