CN114318578A - Antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber and preparation method thereof - Google Patents
Antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber and preparation method thereof Download PDFInfo
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- CN114318578A CN114318578A CN202011152469.9A CN202011152469A CN114318578A CN 114318578 A CN114318578 A CN 114318578A CN 202011152469 A CN202011152469 A CN 202011152469A CN 114318578 A CN114318578 A CN 114318578A
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 130
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 54
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002696 manganese Chemical class 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
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- 238000007873 sieving Methods 0.000 claims abstract description 7
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- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920001661 Chitosan Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001523 electrospinning Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 57
- 239000000463 material Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract description 2
- 238000009987 spinning Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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Abstract
The invention provides a preparation method of an antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber, which comprises the steps of (1) simultaneously dropwise adding a hydrogen peroxide solution and an alkali solution into a manganese salt solution, reacting for 4-8 h, carrying out suction filtration, washing, drying, grinding and sieving on a product to obtain manganese dioxide powder; (2) dissolving solid polyurethane resin in a solvent to obtain a polyurethane solution; uniformly mixing manganese dioxide powder, an antibacterial agent and a liquid coupling agent to obtain a mixture A; adding the mixture A into a polyurethane solution to obtain an electrostatic spinning solution; (3) and preparing the manganese dioxide/polyurethane composite fiber from the electrostatic spinning solution by adopting an electrostatic spinning technology. The manganese dioxide/polyurethane composite fiber prepared by the method not only has long-acting antibacterial performance, but also has the function of removing formaldehyde at room temperature, and has the advantages of simple preparation material acquisition, low cost and simple production process. The invention also provides the manganese dioxide/polyurethane composite fiber for resisting bacteria and removing formaldehyde.
Description
Technical Field
The invention relates to the technical field of electrostatic spinning materials, in particular to an antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber and a preparation method thereof.
Background
The electrostatic spinning technology is a device for spinning by spraying a polymer solution under a strong electric field. The superfine fiber with the diameter ranging from submicron to nanometer can be obtained through electrostatic spinning, and the superfine fiber has the characteristics of large specific surface area, high porosity and the like. The electrostatic spinning method for preparing the inorganic substance and high polymer material composite fiber is a common method, and at present, the antibacterial property of the composite fiber is a research hotspot, for example, Chinese patent CN105887327B discloses a composite nanofiber membrane and a preparation method thereof, which specifically records that chitosan, gelatin and polyurethane are blended, and the electrostatic spinning method is utilized to prepare the antibacterial composite fiber; the chitosan is used as an antibacterial material and is mainly used for medical wound dressings. For example, chinese patent CN106988016B discloses an antibacterial aqueous polyurethane nanofiber membrane and a preparation method thereof, which discloses that nano silver ions, aqueous polyurethane and polyvinyl alcohol are mixed to prepare an antibacterial composite fiber by an electrostatic spinning method, however, silver ions are expensive and easily oxidized and blackened for a long time, and the water resistance of an aqueous material is not particularly good and is limited in application.
At present, formaldehyde is one of the most common and most toxic indoor air pollutants, and mainly comes from furniture, wooden boards and fillers, fabrics, coatings, wallpaper, carpets and even curtains. Long-term, low-concentration formaldehyde exposure can cause symptoms such as headache, hypodynamia, sensory disturbance, immunity reduction and the like, and the world health organization determines that formaldehyde has carcinogenicity, and long-term formaldehyde exposure can increase the probability of suffering from special cancers. Today, the atmospheric environmental pollution is becoming more serious, and how to effectively remove formaldehyde in indoor air pollutants is a scientific difficult problem to be solved urgently.
Manganese dioxide is a novel material for removing formaldehyde, and can effectively decompose pollutants such as formaldehyde in the air at room temperature without any external force. The application focuses on research on the preparation of the composite fiber with formaldehyde removal function by combining manganese dioxide with electrostatic spinning so as to solve the technical problem.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of the manganese dioxide/polyurethane composite fiber for antibiosis and formaldehyde removal, the manganese dioxide/polyurethane composite fiber prepared by the method not only has long-acting antibiosis performance, but also has the function of removing formaldehyde at room temperature, the preparation material is easy to obtain, the cost is low, and the production process is simple.
The invention also aims to provide the manganese dioxide/polyurethane composite fiber for resisting bacteria and removing formaldehyde. In order to realize the aim, the invention provides a preparation method of an antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber, which comprises the following steps:
(1) preparation of manganese dioxide powder
Simultaneously dropwise adding the hydrogen peroxide solution and the aqueous alkali into the manganese salt solution until precipitates are generated, then carrying out reflux stirring reaction for 4-8 h at the temperature of 50-80 ℃, carrying out suction filtration, washing, drying, grinding and sieving on the product to obtain manganese dioxide powder;
(2) preparation of the electrospinning solution
Dissolving solid polyurethane resin in a solvent, and stirring and dissolving to obtain a polyurethane solution;
uniformly mixing manganese dioxide powder, an antibacterial agent and a liquid coupling agent to obtain a mixture A;
adding the mixture A into a polyurethane solution, and uniformly stirring to obtain an electrostatic spinning solution;
(3) and (3) preparing the antibacterial and formaldehyde-removing manganese dioxide/polyurethane composite fiber from the electrostatic spinning solution obtained in the step (2) by adopting an electrostatic spinning technology.
Compared with the prior art, in the preparation method of the antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber, manganese dioxide powder and electrostatic spinning solution are prepared, and the electrostatic spinning technology is combined to prepare the manganese dioxide/polyurethane composite fiber. In addition, the preparation material is easy to obtain, the cost is low, no special environments such as high temperature, high pressure, inert gas and the like exist in the preparation process, and the production process is simple.
Correspondingly, the application also provides an antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber prepared by the preparation method.
Detailed Description
The technical solutions of the present invention are further illustrated by the following specific embodiments, but the present invention is not limited thereto.
The invention provides a preparation method of an antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber, which comprises the following steps:
(1) preparation of manganese dioxide powder
Simultaneously dropwise adding the hydrogen peroxide solution and the aqueous alkali into the manganese salt solution until precipitates are generated, then carrying out reflux stirring reaction for 4-8 h at the temperature of 50-80 ℃, carrying out suction filtration, washing, drying, grinding and sieving on the product to obtain manganese dioxide powder;
(2) preparation of the electrospinning solution
Dissolving solid polyurethane resin in a solvent, and stirring and dissolving to obtain a polyurethane solution;
uniformly mixing manganese dioxide powder, an antibacterial agent and a liquid coupling agent to obtain a mixture A;
adding the mixture A into a polyurethane solution, and uniformly stirring to obtain an electrostatic spinning solution;
(3) and (3) preparing the antibacterial and formaldehyde-removing manganese dioxide/polyurethane composite fiber from the electrostatic spinning solution obtained in the step (2) by adopting an electrostatic spinning technology.
In the step (1), in the preparation method, the manganese salt precursor is used, so that the manganese dioxide is not easy to agglomerate, the specific surface area of the manganese dioxide is increased, the large contact area with formaldehyde is realized, and the formaldehyde removal performance of the manganese dioxide powder can be improved.
Respectively adding manganese salt, alkali and hydrogen peroxide into deionized water to respectively prepare 0.2-2.5 mol/L of the manganese salt aqueous solution, 1-3 mol/L of the alkali solution and 5-15% of the hydrogen peroxide aqueous solution.
Preferably, the manganese salt in the manganese salt solution is selected from at least one of manganese sulfate, manganese chloride and manganese nitrate. When manganese sulfate is adopted, the bonding force and the compatibility are better in the manganese dioxide mixture generated by the reaction.
Preferably, the alkali in the alkali solution is at least one of sodium hydroxide, potassium hydroxide, ammonia water and ammonium bicarbonate.
In the step (2), the solvent is selected from at least one of THF (tetrahydrofuran), DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide), and at least one of toluene and ethyl acetate.
Preferably, the polyurethane resin is thermoplastic polyurethane resin (TPU) with Shore hardness of 60-90A, elongation at break of 400-800% and tensile strength of 15-40 MPa. For example, C60AW by Basff, A885, M180 by Nicotimeri, 69M85U by Baodingtai, T3685, etc. can be used.
Preferably, the temperature is controlled to be 50-90 ℃ when the polyurethane resin is dissolved, and the solid content of the polyurethane solution is preferably 5-20%. Preferably, the proportion of the manganese dioxide powder to the polyurethane is 2-10%.
Preferably, the antibacterial agent is at least one selected from isothiazoline type antibacterial agents, alginates and chitosan. Preferably, an isothiazoline-type antibacterial agent is adopted, and the isothiazoline-type antibacterial agent can be better compatible with the thermoplastic polyurethane resin, and has stronger antibacterial property and long-acting effect. Specifically, the isothiazoline-type antibacterial agent is selected from n-butyl-1, 2-isothiazoline-3-ketone. Preferably, the amount of the antibacterial agent is 10 to 50% of the manganese dioxide powder.
Preferably, the liquid coupling agent is selected from liquid silane coupling agents. As the liquid silane coupling agent, at least one of KH-550, KH-560 and KH-570 can be used. Preferably, the amount of the liquid coupling agent is 10-25% of the manganese dioxide powder.
And (3) putting the electrostatic spinning solution on electrostatic spinning equipment for spinning, wherein the spinning collection mode is flat plate collection or rotary drum collection, and the diameter of the obtained fiber is 20-1000 nm.
Wherein, during electrostatic spinning, the external voltage is 12-30kV, the distance from the spinning needle to the receiving device is 5-30cm, and the flow rate of the spinning solution is 0.1-4.0 mL/h.
The following is a description by way of specific examples, but not limited thereto.
Example 1
A preparation method of antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber comprises the following steps:
(1) preparation of manganese dioxide powder
(1.1) respectively adding manganese sulfate, sodium hydroxide and hydrogen peroxide into deionized water to respectively prepare a manganese salt solution of 2mol/L, an alkali solution of 2mol/L and a hydrogen peroxide solution of 5%;
(1.2) simultaneously dropwise adding the hydrogen peroxide solution and the alkali solution into the manganese salt solution until precipitates are generated, and then refluxing and stirring for reaction for 4 hours at the temperature of 50 ℃ at the rotating speed of 200 rpm;
(1.3) cooling to room temperature, performing suction filtration and washing, removing the filtrate, taking the filtrate, and drying in an oven at 80 ℃ for 24 hours to completely dry;
(1.4) grinding the dried material into powder, and sieving the powder through a 2000-mesh sieve to obtain nano-scale to micron-scale manganese dioxide powder for later use.
(2) Preparation of the electrospinning solution
Dissolving a Pasteur C60AW resin (Shore hardness 64A, elongation at break 800% and tensile strength 30MPa) in a solvent of tetrahydrofuran and toluene, and stirring to dissolve to obtain a polyurethane solution;
uniformly mixing manganese dioxide powder with KH-560, adding chitosan, and uniformly stirring to be viscous to obtain a mixture A;
adding the mixture A into a polyurethane solution, and uniformly stirring to obtain an electrostatic spinning solution;
(3) putting the electrostatic spinning solution on electrostatic spinning equipment for spinning to prepare manganese dioxide/polyurethane composite fiber, wherein: the spinning collection mode is drum collection, the average diameter of the obtained fiber is 100nm, the external voltage is 12kV, the distance from a spinning needle to a receiving device is 10cm, and the flow rate of the spinning solution is 0.1 mL/h.
Example 2
A preparation method of antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber comprises the following steps:
(1) preparation of manganese dioxide powder
(1.1) respectively adding manganese nitrate, ammonium bicarbonate and hydrogen peroxide into deionized water to respectively prepare 1mol/L manganese salt solution, 1mol/L alkali solution and 10% hydrogen peroxide solution;
(1.2) simultaneously dropwise adding the hydrogen peroxide solution and the alkali solution into the manganese salt solution until precipitates are generated, and then refluxing and stirring at 60 ℃ for reaction for 6 hours at the rotating speed of 200 rpm;
(1.3) cooling to room temperature, carrying out suction filtration and washing, removing the filtrate, taking the filtrate, and drying in an oven at 90 ℃ for 24 hours to completely dry the filtrate;
(1.4) grinding the dried material into powder, sieving with a 2000-mesh sieve to obtain nano-scale to micron-scale manganese dioxide powder for later use,
(2) preparation of the electrospinning solution
Dissolving 69M85U resin (Shore hardness 85A, elongation at break 600% and tensile strength 35MPa) of Baodingtai in a solvent of N, N-dimethylformamide and ethyl acetate, and stirring for dissolving to obtain a polyurethane solution;
uniformly mixing manganese dioxide powder with KH-570, then adding alginate, and uniformly stirring to be viscous to obtain a mixture A;
adding the mixture A into a polyurethane solution, and uniformly stirring to obtain an electrostatic spinning solution;
(3) putting the electrostatic spinning solution on electrostatic spinning equipment for spinning to prepare manganese dioxide/polyurethane composite fiber, wherein: the spinning collection mode is drum collection, the average diameter of the obtained fiber is 100nm, the external voltage is 12kV, the distance from a spinning needle to a receiving device is 10cm, and the flow rate of the spinning solution is 0.1 mL/h.
Example 3
A preparation method of antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber comprises the following steps:
(1) preparation of manganese dioxide powder
(1.1) respectively adding manganese chloride, ammonia water and hydrogen peroxide into deionized water to respectively prepare a manganese salt solution of 2.5mol/L, an alkali solution of 3mol/L and a hydrogen peroxide solution of 10%;
(1.2) simultaneously dropwise adding the hydrogen peroxide solution and the alkali solution into the manganese salt solution until precipitates are generated, and then refluxing and stirring at 80 ℃ for reaction for 8 hours at the rotating speed of 200 rpm;
(1.3) cooling to room temperature, performing suction filtration and washing, removing the filtrate, taking the filtrate, and drying in an oven at 80 ℃ for 24 hours to completely dry;
(1.4) grinding the dried material into powder, and sieving the powder through a 2000-mesh sieve to obtain nano-scale to micron-scale manganese dioxide powder for later use.
(2) Preparation of the electrospinning solution
Dissolving A885 resin (Shore hardness 85A, elongation at break 550% and tensile strength 30MPa) of Titaimei in a solvent of N, N-dimethylacetamide and toluene, and stirring for dissolving to obtain a polyurethane solution;
uniformly mixing manganese dioxide powder with KH-550, then adding n-butyl-1, 2-isothiazoline-3-ketone, and uniformly stirring to be viscous to obtain a mixture A;
adding the mixture A into a polyurethane solution, and uniformly stirring to obtain an electrostatic spinning solution;
(3) putting the electrostatic spinning solution on electrostatic spinning equipment for spinning to prepare manganese dioxide/polyurethane composite fiber, wherein: the spinning collection mode is drum collection, the average diameter of the obtained fiber is 100nm, the external voltage is 12kV, the distance from a spinning needle to a receiving device is 10cm, and the flow rate of the spinning solution is 0.1 mL/h.
Example 4
This example is essentially the same as example 1, except that: example 4 the antibacterial agent used was n-butyl-1, 2-isothiazolin-3-one, whereas the antibacterial agent used in example 1 was chitosan, which was the same as in example 1 and will not be described again.
Comparative example 1
This comparative example 1 is essentially the same as example 1, except that: comparative example 1 does not contain chitosan, and the rest is the same as example 1 and will not be described again.
Comparative example 2
This comparative example 2 is substantially the same as example 1 except that: comparative example 2 does not contain manganese dioxide powder, and is the same as example 1, and will not be described.
The manganese dioxide/polyurethane composite fibers obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to formaldehyde removal rate and antibacterial property tests, and the results are shown in Table 1.
Wherein, the formaldehyde removal rate test is carried out by referring to the method of GB/T35239-2017.
The antibacterial performance test is carried out by GB/T21510-2008.
TABLE 1 Formaldehyde removal and antibacterial Properties test results
| Test of | Formaldehyde removal rate (after 6 h) | Antibacterial rate (after 24 h) |
| Example 1 | 96.7％ | 90.8％ |
| Example 2 | 96.9％ | 91.7％ |
| Example 3 | 96.0％ | 95.2％ |
| Example 4 | 96.9％ | 95.1％ |
| Comparative example 1 | 95.8％ | 7.3％ |
| Comparative example 2 | / | 90.5％ |
As can be seen from table 1, the manganese dioxide/polyurethane composite fiber prepared by the preparation method of the present application not only has long-lasting antibacterial performance, but also has the function of removing formaldehyde at room temperature. Wherein the performance of the isothiazoline type antibacterial agent is superior to that of chitosan and alginate.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the best embodiments, the present invention is not limited to the above disclosed embodiments, but should cover various modifications, equivalent combinations, made according to the essence of the present invention.
Claims (9)
1. The preparation method of the antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber is characterized by comprising the following preparation steps:
(1) preparation of manganese dioxide powder
Simultaneously dropwise adding the hydrogen peroxide solution and the aqueous alkali into the manganese salt solution until precipitates are generated, then carrying out reflux stirring reaction for 4-8 h at the temperature of 50-80 ℃, carrying out suction filtration, washing, drying, grinding and sieving on the product to obtain manganese dioxide powder;
(2) preparation of the electrospinning solution
Dissolving solid polyurethane resin in a solvent, and stirring and dissolving to obtain a polyurethane solution;
uniformly mixing manganese dioxide powder, an antibacterial agent and a liquid coupling agent to obtain a mixture A;
adding the mixture A into a polyurethane solution, and uniformly stirring to obtain an electrostatic spinning solution;
(3) and (3) preparing the antibacterial and formaldehyde-removing manganese dioxide/polyurethane composite fiber from the electrostatic spinning solution obtained in the step (2) by adopting an electrostatic spinning technology.
2. The method for preparing manganese dioxide/polyurethane composite fiber with antibacterial and formaldehyde-removing functions as claimed in claim 1, wherein in the step (1), the manganese salt in the manganese salt solution is selected from at least one of manganese sulfate, manganese chloride and manganese nitrate.
3. The method for preparing the antibacterial and formaldehyde-removing manganese dioxide/polyurethane composite fiber according to claim 1, wherein in the step (1), the alkali in the alkali solution is at least one of sodium hydroxide, potassium hydroxide, ammonia water and ammonium bicarbonate.
4. The method for preparing manganese dioxide/polyurethane composite fiber with antibacterial and formaldehyde-removing functions as claimed in claim 1, wherein in the step (2), the solvent is at least one selected from tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide, and at least one selected from toluene and ethyl acetate.
5. The method for preparing the manganese dioxide/polyurethane composite fiber with antibacterial and formaldehyde-removing functions as claimed in claim 1, wherein the polyurethane resin is a thermoplastic polyurethane resin with Shore hardness of 60-90A, elongation at break of 400-.
6. The method of claim 1, wherein the antibacterial agent is at least one selected from isothiazoline type antibacterial agents, alginates, and chitosan.
7. The method of claim 6, wherein the antibacterial agent is n-butyl-1, 2-isothiazolin-3-one.
8. The method for preparing the manganese dioxide/polyurethane composite fiber with antibacterial and formaldehyde-removing functions as claimed in claim 1, wherein the liquid coupling agent is selected from liquid silane coupling agents.
9. An antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber, which is characterized by being prepared by the preparation method of the antibacterial formaldehyde-removing manganese dioxide/polyurethane composite fiber according to any one of claims 1 to 8.
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