Degradable protective clothing and method of making same

Abstract

The application relates to the field of medical protective articles, and particularly discloses a degradable protective clothing and a manufacturing method thereof. The degradable protective clothing comprises, from inside to outside, a polylactic acid nanofiber film, a polycaprolactone fiber film and a polyvinyl alcohol spunlace non-woven fabric in sequence; the polylactic acid nanofiber film comprises the following raw materials in parts by weight: 7-9 parts of polylactic acid, 2-4 parts of a heat-conducting filler, 1-3 parts of graphene aerogel and 1-3 parts of polycaprolactone. The degradable protective clothing has the advantages of heat conduction, good heat dissipation effect, good air permeability and moisture permeability, low heat fatigue of a wearer and high mechanical strength.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of medical protective products, more specifically, it relates to a degradable protective clothing and a manufacturing method thereof. BACKGROUND

[0002] In recent years, with the rapid development of economy and society, modern industry is increasing, and the destruction of nature by human beings is intensifying, and various bacteria and viruses are breeding and spreading. In the highly contagious coronavirus pandemic, the spread of droplets and aerosols poses a great threat to medical personnel and epidemic prevention workers. Disposable medical protective clothing can form a good barrier to eliminate or reduce direct contact and droplet contact between patients and medical personnel, thereby preventing the spread of pathogens.

[0003] At present, the main material of disposable protective clothing on the market is polyethylene and polypropylene. Due to its non-degradability, the main treatment method is incineration or landfill with household garbage, which not only wastes land resources, but also causes serious pollution to air and water resources if not properly treated.

[0004] In the prior art, the Chinese patent application file with the application number CN2021114808907 discloses a kind of full biodegradable material for disposable protective clothing, including the following weight parts of substances: PBAT 28.5-71.5 parts, modified calcium carbonate 25-50 parts, PLA 0-10 parts, PPCU 0-10 parts, dispersing agent 0.1-1.0 parts, composite crosslinking agent 0.2-0.5 parts, and composite antioxidant 0.2-0.5 parts. The disposable protective clothing made can be completely degraded and is environmentally friendly.

[0005] For the related technology in the above, the inventors found that the pores of the degradable disposable protective clothing fabric are small, and the liquid resistance is large, so that when the medical personnel sweat, the transport of hot steam is poor, resulting in heat load. When wearing for a long time, the loss of heat and the generation cannot reach balance, the body heat cannot be normally dissipated, causing heat fatigue, and strong stuffiness under high-intensity work, thereby causing physical discomfort. SUMMARY

[0006] In order to make the degradable disposable protective clothing have heat conductivity, and strong moisture permeability and air permeability, and prevent medical personnel from producing heat fatigue, the present application provides a degradable protective clothing and a manufacturing method thereof.

[0007] In a first aspect, the present application provides a degradable protective clothing, which adopts the following technical solution:

[0008] A degradable protective clothing, from inside to outside, includes a polylactic acid nanofiber membrane, a polycaprolactone fiber membrane, and a polyvinyl alcohol spunlace non-woven fabric in sequence.

[0009] The polylactic acid nanofiber membrane comprises the following raw materials by weight: 7-9 parts of polylactic acid, 2-4 parts of heat-conducting filler, 1-3 parts of graphene aerogel, and 1-3 parts of polycaprolactone.

[0010] By adopting the above technical scheme, since the polyvinyl alcohol spunlace non-woven fabric is made of polyvinyl alcohol fibers through needle punching and other processes, due to the existence of amorphous regions, the polyvinyl alcohol spunlace non-woven fabric has certain moisture permeability, and the polyvinyl alcohol spunlace non-woven fabric is used as the outermost layer and the innermost layer, which has water solubility and biodegradability, polycaprolactone is a biodegradable polymer material, which has good biocompatibility, flexibility and temperature sensitivity, and can significantly improve the skin comfort; the polylactic acid nanofiber membrane is made of polylactic acid and polycaprolactone and other raw materials, polylactic acid has good biocompatibility and biodegradability, and is made of starch provided by renewable plant resources, which can be degraded into water and carbon dioxide under the joint action of water, bacteria and microorganisms, realizing natural green and pollution-free, but due to its brittleness, the mechanical strength is not good, therefore, it is blended and modified with polycaprolactone, polycaprolactone is a synthetic biodegradable and bioabsorbable polymer material, which has excellent tensile properties, biocompatibility and thermal stability, and good compatibility with polylactic acid, the use of the two can significantly improve the mechanical properties of the protective clothing, and the graphene aerogel and the heat-conducting filler are added in the polylactic acid fiber nanomembrane, the heat-conducting filler and the graphene aerogel are uniformly loaded on the surface of the fiber formed by the combination of polylactic acid and polycaprolactone, and a heat-conducting framework is constructed in the fiber membrane, so that the protective clothing has a heat dissipation effect, when the wearer sweats, the heat is quickly dissipated to maintain the comfort of the protective clothing, and the addition of the graphene aerogel and the heat-conducting filler can increase the surface roughness of the fiber membrane, improve the contact angle of the polylactic acid nanofiber membrane, and increase the hydrophobicity, so that the sweat is not easy to adhere to the inner surface of the protective clothing, resulting in that the protective clothing is attached to the skin of the wearer, in addition, the graphene layers between the graphene aerogel have a three-dimensional internet-like structure, and the large porosity makes the graphene aerogel have good moisture permeability and air permeability, so that the protective clothing has good air permeability and moisture permeability, and the wearer feels comfortable and not easy to produce a stuffy feeling, preventing heat fatigue.

[0011] Optionally, the heat-conducting filler comprises hexagonal boron nitride nanosheets and carbon nanotubes in a mass ratio of 1:0.2-0.4.

[0012] By adopting the technical scheme, the hexagonal boron nitride nanosheet has stable chemical properties, high thermal stability, heat resistance and lubricity, can be mutually overlapped in the polylactic acid nanofiber, reduces the adhesion points between the fibers, increases the fiber structure porosity and the pore size, the increased pore and channel are more conducive to the airflow passing, thereby improving the air permeability and moisture permeability, and improving the wearing comfort of the protective clothing, and the addition of the hexagonal boron nitride nanosheet can also increase the surface roughness of the polylactic acid nanofiber film, improve the hydrophobicity of the polylactic acid nanofiber film, and the carbon nanotube has high thermal conductivity and can form a heat conduction network in the polylactic acid nanofiber, thereby improving the heat dissipation effect of the protective clothing.

[0013] Optionally, the heat-conducting filler is pretreated.

[0014] Polyvinyl alcohol is added to distilled water, heated to 90-95 DEG C, and a polyvinyl alcohol aqueous solution with a concentration of 3.5-4wt% is prepared, cooled to 50-55 DEG C, and then acetone is added under stirring, and the heat-conducting filler is added after uniform mixing, and then the mixture is left to stand for 24-26h, and then filtered, and the heat-conducting filler is sequentially soaked in acetone, ethanol and methanol, each time for 12-14h, and then dried at room temperature under reduced pressure, and the volume ratio of acetone to polyvinyl alcohol aqueous solution is 3:4-5.

[0015] By adopting the technical scheme, the heat-conducting filler is not uniformly dispersed in the polylactic acid and polycaprolactone due to the weak interfacial force and poor compatibility of the heat-conducting filler with the polylactic acid and polycaprolactone, which can easily lead to poor mechanical properties of the polylactic acid nanofiber film, and therefore the use of polyvinyl alcohol which has good compatibility with polylactic acid and the pretreatment of the heat-conducting filler with acetone and polyvinyl alcohol can improve the compatibility of the heat-conducting filler with polylactic acid, prevent the heat-conducting filler from agglomerating, and improve the mechanical properties of the polylactic acid nanofiber film, and the use of acetone as a poor solvent can induce phase separation to prepare a metastable polyvinyl alcohol solution capable of forming a porous structure, and then the heat-conducting filler is immersed in the metastable solution system, and the porous structure is formed on the surface of the heat-conducting filler through standing, replacement and drying, thereby obtaining the heat-conducting filler with porous polyvinyl alcohol on the surface, and the heat-conducting filler can increase the porosity of the nanofiber film and improve the air permeability when added to the polylactic acid nanofiber film.

[0016] Optionally, the preparation method of the graphene aerogel is as follows: after the carbon fiber is degummed with acetone, the carbon fiber is carboxylated, mixed with paraffin and graphene oxide aerogel, heated to 80-85 DEG C, vacuum impregnated, heated to 160-170 DEG C, and kept at this temperature for 20-24h, and then cooled to room temperature and freeze-dried, and the mass ratio of the carbon fiber, paraffin and graphene oxide aerogel is 0.1-0.12:8-9:1.

[0017] By adopting the technical scheme, the glue layer on the surface of the carbon fiber is removed by acetone to increase the bonding force between the carbon fiber and the graphene, the carbon fiber surface is carboxylated by concentrated nitric acid to obtain the carbon fiber with surface activity, the graphene oxide aerogel is porous, the pore distribution is uniform, the porosity is high, the graphene sheets are crosslinked into a three-dimensional internet-like structure, the paraffin and the graphene aerogel have good compatibility, because the graphene aerogel has good hydrophobic and lipophilic properties, part of the paraffin is filled in the pores of the graphene oxide aerogel, and the other part of the paraffin is attached to the graphene sheet layer of the graphene oxide aerogel, and the two are in close contact, the graphene is used as a heat-conducting skeleton, the paraffin is used as a phase change material, and the carbon fibers are overlapped in the graphene aerogel, reducing the pore size in the graphene aerogel, so that the graphene aerogel has good wrapping properties for the paraffin and is not easy to leak, the graphene is dispersed and wrapped on the surface of the carbon fiber, the graphene aerogel has a pore structure, and the carbon fiber plays a supporting role in the graphene aerogel, further enhancing the strength and thermal conductivity of the aerogel.

[0018] Optionally, the polyvinyl alcohol spunlace non-woven fabric is connected with an elastic layer on the side away from the polycaprolactone fiber membrane, and the elastic layer comprises BTPE elastomer, 1H, 1H, 2H-perfluoro-1-decene and activated carbon with a mass ratio of 1:0.01-0.1:0.06-0.15.

[0019] By adopting the technical scheme, the BTPE is a biodegradable thermoplastic elastomer prepared by hot melt polycondensation and chain extension, which is composed of crystalline aliphatic saturated polyester prepolymer and amorphous aliphatic saturated polyester prepolymer blocks, and has the characteristics of wide application range, low hardness, high elasticity and the like. The weight loss rate of the BTPE is more than 57% after degradation for 120 days under natural soil environmental conditions. The BTPE, the activated carbon and the 1H, 1H, 2H-perfluoro-1-decene are used to form an elastic layer on the polyvinyl alcohol spunlace non-woven fabric, which can improve the hydrophobicity and tear resistance of the protective clothing, and the activated carbon particles can transfer human heat, disperse sweat on the skin, and also adsorb chemical substances, thereby providing protection.

[0020] In a second aspect, the application provides a manufacturing method of a degradable protective clothing, which adopts the following technical scheme:

[0021] A manufacturing method of a degradable protective clothing, comprising the following steps:

[0022] The polycaprolactone is added into a solvent and stirred uniformly to prepare a spinning solution with a concentration of 20-23 wt%, and then the polyvinyl alcohol spunlace non-woven fabric is used as a base cloth for electrospinning to form a polycaprolactone fiber membrane on the polyvinyl alcohol spunlace non-woven fabric, thereby preparing a surface layer.

[0023] The polylactic acid and polycaprolactone are dried at 50-60℃ for 12-16h, then solvent is added to configure a mixed solution with a concentration of 10-12wt%, the heat-conducting filler and graphene aerogel are added and mixed to prepare a mixed spinning solution, the surface layer is used as a base cloth, electrospinning is performed to form a polylactic acid nanofiber film on the polycaprolactone fiber film, and a protective fabric is prepared.

[0024] The protective fabric is cut and sewn, a zipper and a closing edge are installed, and a degradable protective clothing is prepared.

[0025] By adopting the above technical scheme, the polycaprolactone is dissolved and electrospun on the polyvinyl alcohol spunlace non-woven fabric to form a polycaprolactone fiber film, then the polyvinyl alcohol spunlace non-woven fabric and the polycaprolactone fiber film are used as a base, the polylactic acid nanofiber film is formed on the polycaprolactone fiber film by electrospinning, the polylactic acid nanofiber film has a continuous heat-conducting framework penetrating through, is moisture-permeable and air-permeable, does not burden the environment, and has good comfort.

[0026] Optionally, the BTPE elastomer is dissolved in cyclohexanone to prepare a solution with a concentration of 18-20wt%, active carbon and 1H, 1H, 2H-perfluoro-1-decene are added, and after stirring, the solution is coated on the side of the polyvinyl alcohol spunlace non-woven fabric away from the polycaprolactone fiber film, dried at 80-90℃, and then ultraviolet crosslinked for 0.5-1h.

[0027] By adopting the above technical scheme, after ultraviolet irradiation, the C=C groups on the BTPE elastomer are broken to form -C=O and other polar groups with oxygen atoms in the air, thereby crosslinking reaction occurs, and an elastic layer with strong adhesion and high elasticity is formed on the polyvinyl alcohol spunlace non-woven fabric, thereby improving the tear resistance of the protective clothing, the 1H, 1H, 2H-perfluoro-1-decene contained in the elastic layer can improve the hydrophobicity of the elastic layer and improve the surface water resistance of the protective clothing, and the active carbon can increase the filtration efficiency of the protective clothing and improve the air permeability and moisture permeability.

[0028] Optionally, the electrospinning parameters of the polycaprolactone fiber film are as follows: positive voltage 26-30kv, negative voltage 1.5-1.7kv, spinning solution flow rate 0.06-0.08mm / min, receiving distance 18-20cm, and spinning time 10-12min.

[0029] By adopting the above technical scheme, a polycaprolactone fiber film with uniform thickness can be formed on the polyvinyl alcohol spunlace non-woven fabric, thereby improving the stress of the protective clothing.

[0030] Optionally, the electrospinning parameters of the polylactic acid nanofiber membrane are: positive voltage 25-28kv, negative voltage 1.5-1.7kv, mixed spinning solution flow rate 0.07-0.1mm / min, receiving distance 18-20cm, and spinning time 2.5-3h.

[0031] Optionally, the solvent comprises chloroform and DMF in a mass ratio of 7-9:1-3.

[0032] In summary, the present application has the following beneficial effects:

[0033] 1. Since the present application adopts water-soluble polyvinyl alcohol spunlace non-woven fabric, and polycaprolactone fiber membrane as the intermediate layer, and polylactic acid nanofiber membrane as the inner layer in contact with the skin, all three layers are green and degradable, and will not burden the environment. Moreover, graphene aerogel and thermal conductive filler are added to the polylactic acid nanofiber membrane to form a thermal conductive framework, which dissipates body heat through heat conduction to maintain the comfort of the protective clothing, and also allows moisture and air to pass through, preventing water penetration and filtration.

[0034] 2. In the present application, polyvinyl alcohol and acetone are preferably used to pretreat the thermal conductive filler to form a porous structure of polyvinyl alcohol on the thermal conductive filler, which not only improves the compatibility of the thermal conductive filler with polylactic acid, increases the dispersibility of the thermal conductive filler, and improves the mechanical strength of the polylactic acid nanofiber membrane, but also increases the air permeability of the polylactic acid nanofiber membrane due to the porous structure of the thermal conductive filler on the surface, thereby further improving the air and moisture permeability of the protective clothing.

[0035] 3. In the present application, a mixed solution formed by BTPE, activated carbon and 1H,1H,2H-perfluoro-1-decene is preferably coated on the polyvinyl alcohol spunlace non-woven fabric to form an elastic layer on the polyvinyl alcohol spunlace non-woven fabric, which improves the moisture resistance of the surface of the protective clothing and prevents water or blood from penetrating. DETAILED DESCRIPTION

[0036] Preparation Examples 1-4 of graphene aerogel

[0037] Preparation Example 1: Carbon fibers were added to acetone, soaked for 30min, washed, and carboxylated by adding concentrated nitric acid, filtered, washed, dried, mixed with paraffin and graphene oxide aerogel, heated to 80℃, vacuum impregnated, then heated to 160℃, and kept at this temperature for 24h, cooled to room temperature, and freeze-dried. The mass ratio of carbon fibers, paraffin and graphene oxide aerogel was 0.12:8:1.

[0038] Preparation Example 2: Carbon fibers were added to acetone, soaked for 30 min, washed, carboxylated by adding concentrated nitric acid, filtered, washed, dried, mixed with paraffin and graphene oxide aerogel, heated to 85℃, vacuum impregnated, then heated to 170℃, and kept for 20 h, cooled to room temperature, and freeze-dried, the mass ratio of carbon fibers, paraffin and graphene oxide aerogel being 0.1:9:1.

[0039] Preparation Example 3: Paraffin and graphene oxide aerogel were mixed, heated to 85℃, vacuum impregnated, and then freeze-dried, the mass ratio of paraffin and graphene oxide aerogel being 9:1.

[0040] Preparation Example 4: Carbon fibers were added to acetone, soaked for 30 min, washed, carboxylated by adding concentrated nitric acid, filtered, washed, dried, mixed with graphene oxide aerogel, vacuum impregnated, then heated to 160℃, and kept for 24 h, cooled to room temperature, and freeze-dried, the mass ratio of carbon fibers and graphene oxide aerogel being 0.12:1.

[0041] Example

[0042] Example 1: A degradable protective clothing, from inside to outside, includes a polylactic acid nanofiber membrane, a polycaprolactone fiber membrane and a polyvinyl alcohol spunlace non-woven fabric in turn, the specification of the polyvinyl alcohol spunlace non-woven fabric is 30g / m2, the raw material of the polylactic acid nanofiber membrane includes 9kg of polylactic acid, 4kg of thermal conductive filler, 3kg of graphene aerogel and 1kg of polycaprolactone, the polylactic acid is selected from Yisike, with an average molecular weight of 150,000, the polycaprolactone is selected from Haeser Plastics, with an average molecular weight of 50,000, the graphene aerogel is made by Preparation Example 1, and the thermal conductive filler includes hexagonal boron nitride nanosheets and carbon nanotubes with a mass ratio of 1:0.4.

[0043] The above method for making the degradable protective clothing includes the following steps:

[0044] S1, polycaprolactone is added to a solvent and stirred uniformly to prepare a spinning solution with a concentration of 23wt%, a polyvinyl alcohol spunlace non-woven fabric is used as a base fabric, electrospinning is performed to form a polycaprolactone fiber membrane on the polyvinyl alcohol spunlace non-woven fabric to make a surface layer, the polycaprolactone is selected from Haeser Plastics, with an average molecular weight of 50,000, the solvent includes chloroform and DMF with a mass ratio of 7:3, the electrospinning parameters are as follows: positive voltage is 26kv, negative voltage is 1.5kv, spinning solution flow rate is 0.06mm / min, receiving distance is 18cm, and spinning time is 10min;

[0045] S2, drying polylactic acid and polycaprolactone at 60℃ for 12h, then adding solvent, configuring mixed solution with concentration of 12wt%, adding heat-conducting filler and graphene aerogel, mixing uniformly, preparing mixed spinning solution, taking the surface layer prepared in S1 as base cloth, electrospinning, forming polylactic acid nanofiber film on polycaprolactone fiber film, and preparing protective fabric;

[0046] S3, cutting and sewing the protective fabric, installing zipper and closing, and preparing degradable protective clothing, the solvent includes chloroform and DMF with mass ratio of 7:3, the electrospinning parameters are as follows: positive voltage 25kv, negative voltage 1.5kv, flow rate of mixed spinning solution 0.07mm / min, receiving distance 18cm, and spinning time 2.5h;

[0047] Embodiment 2: a degradable protective clothing, which sequentially includes polyvinyl alcohol water-jet non-woven fabric, polycaprolactone fiber film, polylactic acid nanofiber film, polycaprolactone fiber film and polyvinyl alcohol water-jet non-woven fabric, the specification of the polyvinyl alcohol water-jet non-woven fabric is 30g / m 2 , the raw material of the polylactic acid nanofiber film includes 7kg polylactic acid, 2kg heat-conducting filler, 1kg graphene aerogel and 3kg polycaprolactone, the graphene aerogel is prepared by the preparation example 2, and the heat-conducting filler includes hexagonal boron nitride nanosheet and carbon nanotube with mass ratio of 1:0.2.

[0048] The manufacturing method of the degradable protective clothing, including the following steps:

[0049] S1, adding polycaprolactone into solvent, stirring uniformly, preparing spinning solution with concentration of 20wt%, taking polyvinyl alcohol water-jet non-woven fabric as base cloth, electrospinning, forming polycaprolactone fiber film on the polyvinyl alcohol water-jet non-woven fabric, and preparing surface layer, the polycaprolactone is selected from Hease plastic, the average molecule is 50,000, the solvent includes chloroform and DMF with mass ratio of 9:1, the electrospinning parameters are as follows: positive voltage 30kv, negative voltage 1.7kv, flow rate of spinning solution 0.08mm / min, receiving distance 20cm, and spinning time 12min;

[0050] S2, drying polylactic acid and polycaprolactone at 60℃ for 12h, then adding solvent, configuring mixed solution with concentration of 12wt%, adding heat-conducting filler and graphene aerogel, mixing uniformly, preparing mixed spinning solution, taking the surface layer prepared in S1 as base cloth, electrospinning, forming polylactic acid nanofiber film on polycaprolactone fiber film, and preparing protective fabric;

[0051] S3, cutting and sewing the protective fabric, installing the zipper and closing the opening, obtaining the degradable protective clothing, the solvent includes chloroform and DMF with a mass ratio of 9:1, and the electrospinning parameters are: positive voltage 28 kv, negative voltage 1.7 kv, mixed spinning solution flow rate 0.1 mm / min, receiving distance 20 cm, and spinning time 3 h;

[0052] Example 3: A degradable protective clothing, which is different from example 1 in that the graphene aerogel is prepared from preparation example 3.

[0053] Example 4: A degradable protective clothing, which is different from example 1 in that the graphene aerogel is prepared from preparation example 4.

[0054] Example 5: A degradable protective clothing, which is different from example 1 in that the heat-conducting filler is carbon nanotubes, and no hexagonal boron nitride nanosheet is added.

[0055] Example 6: A degradable protective clothing, which is different from example 1 in that the heat-conducting filler is pretreated as follows: polyvinyl alcohol is added to distilled water, heated to 95 ℃, and a polyvinyl alcohol aqueous solution with a concentration of 4 wt% is prepared, cooled to 55 ℃, and then acetone is added under stirring, the mixture is uniformly mixed, and then the heat-conducting filler is added, and the mixture is left to stand for 26 h, and then the heat-conducting filler is filtered, and then the heat-conducting filler is sequentially soaked in acetone, ethanol and methanol for 12 h each time, and then dried under reduced pressure at room temperature, and the volume ratio of acetone to the polyvinyl alcohol aqueous solution is 3:4.

[0056] Example 7: A degradable protective clothing, which is different from example 6 in that the polyvinyl alcohol spunlace non-woven fabric on both sides of the polylactic acid nanofiber membrane is connected to the side away from the polycaprolactone fiber membrane of an elastic layer, and the elastic layer includes BTPE elastomer, 1H, 1H, 2H-perfluoro-1-decene and activated carbon with a mass ratio of 1:0.1:0.15; and the preparation method of the degradable protective clothing is as follows: S1, polycaprolactone is added to a solvent and stirred uniformly to prepare a spinning solution with a concentration of 23 wt%, and a polyvinyl alcohol spunlace non-woven fabric is used as a base fabric, and electrospinning is performed to form a polycaprolactone fiber membrane on the polyvinyl alcohol spunlace non-woven fabric to prepare a surface layer, and the polycaprolactone is selected from Heese Plastic, and the average molecular weight is 50,000, and the solvent includes chloroform and DMF with a mass ratio of 7:3, and the electrospinning parameters are: positive voltage 26 kv, negative voltage 1.5 kv, spinning solution flow rate 0.06 mm / min, receiving distance 18 cm, and spinning time 10 min;

[0057] S2, polylactic acid and polycaprolactone are dried at 60℃ for 12h, then solvent is added to prepare a mixture with a concentration of 12wt%, conductive filler and graphene aerogel are added and mixed to prepare a mixed spinning solution, the surface layer prepared in S1 is used as a base cloth, electrospinning is performed to form a polylactic acid nanofiber film on the polycaprolactone fiber film, the solvent includes chloroform and DMF in a mass ratio of 7:3, the electrospinning parameters are: positive voltage 25kv, negative voltage 1.5kv, the flow rate of the mixed spinning solution is 0.07mm / min, the receiving distance is 18cm, and the spinning time is 2.5h;

[0058] S3, the BTPE elastomer is dissolved in cyclohexanone to prepare a solution with a concentration of 20wt%, activated carbon and 1H, 1H, 2H-perfluoro-1-decene are added, after stirring, the polyvinyl alcohol spunlace non-woven fabric obtained in step S2 is coated on the side away from the polycaprolactone fiber film, dried at 80℃, and then ultraviolet crosslinked for 1h to prepare a protective fabric;

[0059] S4, the protective fabric is cut and sewn, and a zipper and a closing edge are installed to prepare a degradable protective clothing.

[0060] Example 8: A degradable protective clothing, which differs from example 7 in that the elastic layer comprises BTPE elastomer, 1H, 1H, 2H-perfluoro-1-decene and activated carbon in a mass ratio of 1:0.01:0.06.

[0061] Example 9: A degradable protective clothing, which differs from example 7 in that the elastic layer comprises BTPE elastomer and 1H, 1H, 2H-perfluoro-1-decene in a mass ratio of 1:0.01.

[0062] Example 10: A degradable protective clothing, which differs from example 7 in that the elastic layer comprises BTPE elastomer and activated carbon in a mass ratio of 1:0.06.

[0063] Comparative Example

[0064] Comparative Example 1: A degradable protective clothing, which differs from example 1 in that no graphene aerogel is added.

[0065] Comparative Example 2: A degradable protective clothing, which differs from example 1 in that no conductive filler is added.

[0066] Comparative Example 3: A method for preparing a degradable protective clothing, comprising the following steps: (1) drying polylactic acid masterbatch, polycaprolactone masterbatch and polyethylene masterbatch; (2) feeding the dried polylactic acid masterbatch, polycaprolactone masterbatch and polyethylene masterbatch into a screw extruder for melt extrusion respectively; (3) mixing the melt according to 70 parts by weight of polylactic acid, 20 parts by weight of polycaprolactone and 10 parts by weight of polyethylene, and then extruding from a spinning plate, and then drawing by airflow to a web laying machine, with the grammage controlled at about 80 g / m2and the fiber diameter controlled at about 6 microns; (4) after webbing, reinforcing by needle punching to obtain a non-woven fabric; (5) according to the design specifications, cutting and sewing the non-woven fabric by a conventional method to obtain a degradable protective clothing.

[0067] Performance detection test

[0068] The protective clothing was prepared according to the method in the examples and comparative examples, and the performance of the protective clothing was detected according to the following method, and the detection results are recorded in Table 1.

[0069] 1. Stress: the mechanical properties of the protective clothing were detected by an electronic tensile testing machine;

[0070] 2. Degradation rate: according to ISO 16929 standard, composting for 180 days, removing the zipper and lock buckle before degradation, and taking the weight loss rate as the degradation rate;

[0071] 3. Thermal conductivity: the thermal conductivity of the protective clothing was tested by a Hot Disk TPS 2500S thermal conductivity instrument;

[0072] 4. Moisture permeability and air permeability: the moisture permeability of the protective clothing was detected by a W3 / 031 water vapor permeability tester, and 3 positions on each front and back surface of the protective clothing were tested to take the average value; the air permeability of the protective clothing was tested by a YG461E-III full-automatic air permeability tester, and the test pressure difference was 100 Pa, and the test was carried out under constant temperature and humidity, and the average value of 5 test results was taken as the test result;

[0073] 5. Surface moisture resistance: detected according to GB / T19082-2009 "Technical requirements for medical disposable protective clothing".

[0074] Table 1: Performance detection results of degradable protective clothing

[0075]

[0076]

[0077] In Example 1 and Example 2, hexagonal boron nitride nanosheets and carbon nanotubes were used as thermal conductive fillers, and polylactic acid and polycaprolactone were used as main materials, and the prepared protective clothing had good biodegradation rate, good mechanical properties, good moisture permeability and air permeability, high thermal conductivity, and could prevent the wearer from producing heat stress.

[0078] The graphene aerogel prepared in Preparation Example 3 is used in Example 3, and the graphene aerogel prepared in Preparation Example 4 is used in Comparative Example 4. The air permeability and moisture permeability of the protective clothing prepared in Example 3 are increased, but the thermal conductivity is decreased. The air permeability, moisture permeability and stress of the protective clothing prepared in Example 4 are all decreased, which indicates that the paraffin as a phase change material can increase the heat absorption of the protective clothing and improve the thermal conductivity, but it can also decrease the porosity of the graphene aerogel, and thus the air permeability and moisture permeability are decreased. The carbon fiber can increase the porosity of the graphene aerogel, and thus the air permeability and moisture permeability are increased.

[0079] Example 5 uses carbon nanotubes as the thermal conductive filler. As shown in Table 1, the thermal conductivity of the protective clothing prepared in Example 5 is decreased, the air permeability and moisture permeability are decreased, but the stress is improved, which indicates that the addition of the hexagonal boron nitride nanosheet increases the porosity between the nanofibers, and the increased porosity and channels are beneficial to the airflow, and thus the air permeability and moisture permeability are increased.

[0080] The thermal conductive filler in Example 6 is pretreated by polyvinyl alcohol. Compared with Example 1, the stress of the protective clothing prepared in Example 6 is improved, and the moisture permeability and air permeability are increased, which indicates that the pretreatment by polyvinyl alcohol improves the compatibility of the thermal conductive filler with the polylactic acid matrix, and thus the stress is improved, and the air permeability and moisture permeability are improved.

[0081] Compared with Example 6, Examples 7 and 8 further coat an elastic layer made of BTPE and activated carbon on the side of the polyvinyl alcohol spunlace non-woven fabric away from the polycaprolactone fiber membrane on both sides of the protective clothing. As shown in Table 1, the stress of the protective clothing prepared in Examples 7 and 8 is increased, the air permeability and moisture permeability are improved, and the surface moisture resistance grade is improved.

[0082] Compared with Example 7, Examples 9 and 10 do not add activated carbon and 1H, 1H, 2H-perfluoro-1-decene in the elastic layer, respectively. The surface moisture resistance grade of the protective clothing prepared in Example 9 is unchanged, the air permeability is decreased, the surface moisture resistance of the protective clothing prepared in Example 10 is decreased, the surface hydrophobicity is decreased, and the moisture permeability is decreased.

[0083] Comparative Example 1 does not add graphene aerogel, and Comparative Example 2 does not add thermal conductive filler. Compared with Example 1, the thermal conductivity of the protective clothing prepared in Comparative Examples 1 and 2 is decreased, and the air permeability and moisture permeability are decreased.

[0084] Comparative Example 3 is a protective clothing prepared by polylactic acid and polycaprolactone in the prior art. The thermal conductivity is poor, the air permeability and moisture permeability are insufficient, the sweat of the wearer is difficult to discharge, and the comfort is poor.

[0085] The embodiments are only illustrative of the present application, and are not intended to limit the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A biodegradable protective suit, characterized in that, From the inside out, it consists of polylactic acid nanofiber membrane, polycaprolactone fiber membrane, and polyvinyl alcohol spunlace nonwoven fabric. The polylactic acid nanofiber membrane comprises the following raw materials in parts by weight: 7-9 parts polylactic acid, 2-4 parts thermally conductive filler, 1-3 parts graphene aerogel, and 1-3 parts polycaprolactone. The thermally conductive filler is pretreated: Polyvinyl alcohol is added to distilled water and heated to 90-95℃ to prepare a 3.5-4wt% polyvinyl alcohol aqueous solution. The solution is then cooled to 50-55℃, and acetone is added while stirring. After mixing evenly, thermally conductive filler is added and allowed to stand for 24-26 hours. The solution is then filtered, and the thermally conductive filler is sequentially immersed in acetone, ethanol, and methanol for 12-14 hours each time. The solution is then dried under reduced pressure at room temperature. The volume ratio of acetone to polyvinyl alcohol aqueous solution is 3:4-5.

2. The biodegradable protective clothing according to claim 1, characterized in that: The thermally conductive filler comprises hexagonal boron nitride nanosheets and carbon nanotubes in a mass ratio of 1:0.2-0.

4.

3. The biodegradable protective clothing according to claim 1, characterized in that, The preparation method of the graphene aerogel is as follows: carbon fiber is degummed with acetone and then carboxylated, mixed with paraffin and graphene oxide aerogel, heated to 80-85℃, vacuum impregnated, heated to 160-170℃, kept at this temperature for 20-24h, cooled to room temperature, and freeze-dried. The mass ratio of carbon fiber, paraffin and graphene oxide aerogel is 0.1-0.12:8-9:

1.

4. The biodegradable protective clothing according to claim 1, characterized in that, An elastic layer is attached to the side of the polyvinyl alcohol spunlace nonwoven fabric away from the polycaprolactone fiber membrane. The elastic layer includes BTPE elastomer, 1H,1H,2H-perfluoro-1-decene, and activated carbon in a mass ratio of 1:0.01-0.1:0.06-0.

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5. The method for manufacturing the biodegradable protective clothing according to any one of claims 1-4, characterized in that, Includes the following steps: Polycaprolactone is added to a solvent and stirred evenly to prepare a spinning solution with a concentration of 20-23 wt%. Polyvinyl alcohol spunlace nonwoven fabric is used as the base fabric and electrospun to form a polycaprolactone fiber film on the polyvinyl alcohol spunlace nonwoven fabric to make the surface layer. Polylactic acid and polycaprolactone are dried at 50-60℃ for 12-16h, then a solvent is added to prepare a mixed solution with a concentration of 10-12wt%. Thermally conductive filler and graphene aerogel are added and mixed to obtain a mixed spinning solution. Using the surface layer as the base fabric, electrospinning is performed to form a polylactic acid nanofiber membrane on the polycaprolactone fiber membrane to obtain a protective fabric. The protective fabric is cut and sewn, and zippers and closures are installed to produce a biodegradable protective garment.

6. The method for manufacturing the biodegradable protective clothing according to claim 5, characterized in that, It also includes the following steps: BTPE elastomer was dissolved in cyclohexanone to prepare a solution with a concentration of 18-20 wt%. Activated carbon and 1H,1H,2H-perfluoro-1-decene were added and stirred evenly. The solution was then coated onto the side of polyvinyl alcohol spunlace nonwoven fabric away from the polycaprolactone fiber membrane and dried at 80-90℃. Then, it was UV crosslinked for 0.5-1 h.

7. The method for manufacturing the biodegradable protective clothing according to claim 5, characterized in that, The electrospinning parameters for the polycaprolactone fiber membrane are as follows: positive voltage of 26-30 kV, negative voltage of 1.5-1.7 kV, spinning solution flow rate of 0.06-0.08 mm / min, receiving distance of 18-20 cm, and spinning time of 10-12 min.

8. The method for manufacturing the biodegradable protective clothing according to claim 5, characterized in that, The electrospinning parameters for the polylactic acid nanofiber membrane are: positive voltage 25-28 kV, negative voltage 1.5-1.7 kV, mixed spinning solution flow rate 0.07-0.1 mm / min, receiving distance 18-20 cm, and spinning time 2.5-3 h.

9. The method for manufacturing the biodegradable protective clothing according to claim 5, characterized in that, The solvent comprises chloroform and DMF in a mass ratio of 7-9:1-3.

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