CN116814146A - Graphene-based antibacterial and wear-resistant automotive interior leather and preparation method thereof - Google Patents
Graphene-based antibacterial and wear-resistant automotive interior leather and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 123
- 239000010985 leather Substances 0.000 title claims abstract description 62
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims description 100
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 150000003378 silver Chemical class 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000007795 chemical reaction product Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000000839 emulsion Substances 0.000 claims description 21
- 229920002635 polyurethane Polymers 0.000 claims description 21
- 239000004814 polyurethane Substances 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 7
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims 2
- 241000894006 Bacteria Species 0.000 abstract description 8
- 238000009395 breeding Methods 0.000 abstract description 2
- 230000001488 breeding effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 244000063299 Bacillus subtilis Species 0.000 description 2
- 235000014469 Bacillus subtilis Nutrition 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000005496 phosphonium group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 241000700605 Viruses Species 0.000 description 1
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- 238000005119 centrifugation Methods 0.000 description 1
- OBTIDFCSHQLONE-UHFFFAOYSA-N diphenylphosphane;lithium Chemical compound [Li].C=1C=CC=CC=1PC1=CC=CC=C1 OBTIDFCSHQLONE-UHFFFAOYSA-N 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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Abstract
The invention relates to the field of automobile interior leather, in particular to an antibacterial and wear-resistant automobile interior leather based on graphene and a preparation method thereof, which are used for solving the problem that the existing automobile interior leather is poor in antibacterial property and wear resistance; according to the preparation method, the modified silver-containing graphene is sprayed onto the surface of the automobile interior leather, so that the automobile interior leather is endowed with good wear resistance, the automobile interior leather can be effectively protected, damage of the automobile interior leather due to friction and scratch is avoided, the service life of the automobile interior leather is prolonged, the modified silver-containing graphene can endow the automobile interior leather with good antibacterial property, bacteria are prevented from breeding and even adhering bacteria are eliminated, the probability of contact between people and bacteria is reduced, and the probability of illness of people is reduced.
Description
Technical Field
The invention relates to the field of automobile interior leather, in particular to an antibacterial and wear-resistant automobile interior leather based on graphene and a preparation method thereof.
Background
The automobile interior trim mainly refers to automobile products used for refitting the inside of an automobile, and relates to aspects of the inside of the automobile, such as automobile steering wheel sleeves, automobile cushions, automobile foot pads, automobile perfumes, automobile pendants, internal ornaments, storage boxes and the like, which are automobile interior trim products.
Therefore, the automotive interior leather is one of important materials in the interior of an automobile, however, the automotive interior leather is easy to wear and damage due to long-time use and contact, the overall beauty of the leather is affected, and the automotive interior leather is also easy to be affected by microorganisms such as bacteria and viruses, so that the problems of peculiar smell, decay and the like are caused.
How to improve the antibacterial and wear-resistant properties of the existing automotive interior leather is not good, so that an automotive interior leather based on graphene and a preparation method thereof are needed to solve the problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide an antibacterial and wear-resistant automotive interior leather based on graphene and a preparation method thereof: adding modified silver-containing graphene into polyurethane emulsion, performing ultrasonic treatment to obtain graphene dispersion liquid, adding the graphene dispersion liquid into deionized water, stirring and reacting to obtain graphene spraying liquid, spraying the graphene spraying liquid onto the surface of automobile interior leather, and drying to obtain the antibacterial and wear-resistant automobile interior leather based on graphene, thereby solving the problem of poor antibacterial and wear-resistant properties of the existing automobile interior leather.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of graphene-based antibacterial and wear-resistant automotive interior leather comprises the following steps:
step one: weighing 2-12 parts of modified silver-containing graphene, 20-25 parts of polyurethane emulsion and 55-65 parts of deionized water according to parts by weight for standby;
step two: adding modified silver-containing graphene into polyurethane emulsion, and performing ultrasonic treatment on the polyurethane emulsion for 15 to 20min under the condition that the ultrasonic power is 300 to 350W to obtain graphene dispersion liquid;
step three: adding the graphene dispersion liquid into deionized water, and then stirring and reacting for 0.5-1h under the conditions that the temperature is 35-45 ℃ and the stirring speed is 400-500r/min to obtain graphene spraying liquid;
step four: and (3) spraying the graphene spraying liquid onto the surface of the automobile interior leather, wherein the spraying amount is 10-15g/sf, and drying to obtain the graphene-based antibacterial and wear-resistant automobile interior leather.
As a further scheme of the invention: the polyurethane emulsion is aqueous polyurethane emulsion PU-402, and the solid content is 50%.
As a further scheme of the invention: the modified silver-containing graphene is prepared by the following steps:
step s1: adding graphite powder and sodium nitrate into a three-neck flask with a stirrer and a thermometer, adding concentrated sulfuric acid while stirring at the temperature of-5-0 ℃ and the stirring rate of 400-500r/min, continuing to stir and react for 0.5-1h after adding potassium permanganate, continuing to stir and react for 0.5-1h, then heating to 35-40 ℃ and continuing to stir and react for 2-3h, adding deionized water and heating to 90-95 ℃ and continuing to stir and react for 2-3h, pouring the reaction product into hydrogen peroxide solution after the reaction, standing and precipitating, vacuum filtering, washing a filter cake with hydrochloric acid solution and distilled water for 3-5 times sequentially, then placing in a vacuum drying oven, and drying for 6-8h at the temperature of 60-65 ℃ to obtain graphene oxide;
step s2: adding graphene oxide and deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, performing ultrasonic treatment for 2-3 hours under the condition that the ultrasonic power is 300-350W, then adding silver nitrate solution dropwise under the condition that the temperature is 25-30 ℃ and the stirring rate is 400-500r/min, controlling the dropping rate to be 1-2 drops/s, continuing to stir and react for 2-2.5 hours after the dropping, then adding sodium borohydride solution dropwise under the condition that the stirring rate is 1-2 drops/s, continuing to stir and react for 5-6 hours after the dropping, centrifuging a reaction product after the reaction is finished, washing a precipitate with distilled water for 3-5 times, then placing the precipitate in a vacuum drying box, and drying the precipitate for 3-5 hours under the condition that the temperature is 60-65 ℃ to obtain silver-containing graphene;
step s3: adding triphenylphosphine, potassium tert-butoxide, lithium and tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring at a temperature of-5-0 ℃ and a stirring rate of 400-500r/min for reacting for 20-30 min, heating to 35-40 ℃ for continuously stirring for reacting for 8-10h, cooling to-5-0 ℃ for continuously stirring for reacting for 2-3h, heating to 10-15 ℃ for continuously stirring while dropwise adding 1, 4-dibromobutane, controlling a dropping rate to 1-2 drops/s, continuously stirring for reacting for 5-6h after the dropping is finished, cooling the reaction product to room temperature after the reaction is finished, then rotationally evaporating to remove the solvent, washing with hydrochloric acid solution, distilled water and absolute methanol for 2-3 times sequentially, and then recrystallizing with chloroform to obtain an intermediate 1;
the reaction principle is as follows:
step s4: adding the intermediate 1, 3-bromo-1-propanol and chloroform into a three-neck flask provided with a thermometer, a stirrer and an air duct, introducing nitrogen for protection, stirring for reaction at the temperature of 25-30 ℃ and the stirring rate of 400-500r/min for 15-20min, heating to 60-65 ℃ for continuous stirring for reaction for 40-50h, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, and recrystallizing with ethyl acetate to obtain an intermediate 2;
the reaction principle is as follows:
step s5: adding the intermediate 2, diphenylmethane diisocyanate, dibutyltin dilaurate and methylene dichloride into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 0.5-1h under the conditions of 25-30 ℃ and stirring speed of 400-500r/min, heating to reflux, continuing stirring and reacting for 6-8h, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, and recrystallizing with ethyl acetate to obtain the antibacterial connecting agent;
the reaction principle is as follows:
step s6: adding silver-containing graphene, N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, performing ultrasonic treatment for 2-3 hours under the condition of ultrasonic power of 300-350W, adding an antibacterial connecting agent and dibutyltin dilaurate to continue ultrasonic treatment for 5-10 min, introducing nitrogen for protection, stirring at the temperature of 25-30 ℃ and the stirring rate of 400-500r/min for reacting for 0.5-1 hour, heating to reflux for continuing stirring for reacting for 8-10 hours, cooling the reaction product to room temperature after the reaction is finished, centrifuging, washing the precipitate with dichloromethane for 3-5 times, and then placing in a vacuum drying box, and drying at the temperature of 40-45 ℃ for 10-15 hours to obtain the modified silver-containing graphene.
As a further scheme of the invention: the dosage ratio of the graphite powder, sodium nitrate, concentrated sulfuric acid, potassium permanganate and deionized water in the step s1 is 1g:0.5-0.8g:20-25mL:3-4g:45-50mL, wherein the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the hydrogen peroxide solution is 30%, and the mass fraction of the hydrochloric acid solution is 8-10%.
As a further scheme of the invention: the dosage ratio of the graphene oxide, deionized water, silver nitrate solution and sodium borohydride solution in the step s2 is 0.1g:80-100mL:20-30mL:3-5mL, wherein the molar concentration of the silver nitrate solution is 0.1-0.2mol/L, and the mass fraction of the sodium borohydride solution is 10-12%.
As a further scheme of the invention: the triphenylphosphine, potassium tert-butoxide, lithium, tetrahydrofuran, ammonium chloride and 1, 4-dibromobutane in step s3 were used in an amount ratio of 0.1mol:0.8-1.2g:0.2-0.22mol:80-100mL:0.11-0.13mol:0.05mol, wherein the mass fraction of the hydrochloric acid solution is 8-10%.
As a further scheme of the invention: the ratio of the amount of intermediate 1, 3-bromo-1-propanol and chloroform in step s4 was 0.1mol:0.22-0.25mol:120-150mL.
As a further scheme of the invention: the ratio of the intermediate 2, diphenylmethane diisocyanate, dibutyltin dilaurate and methylene chloride in step s5 is 10mmol:20mmol:0.1-0.15g:40-50mL.
As a further scheme of the invention: the dosage ratio of the silver-containing graphene, the N, N-dimethylformamide, the antibacterial connecting agent and the dibutyltin dilaurate in the step s6 is 1g:120-150mL:0.5-1.5g:0.005-0.01g.
As a further scheme of the invention: the graphene-based antibacterial and wear-resistant automotive interior leather is prepared according to the preparation method of the graphene-based antibacterial and wear-resistant automotive interior leather.
The invention has the beneficial effects that:
according to the graphene-based antibacterial and wear-resistant automotive interior leather and the preparation method thereof, modified silver-containing graphene is added into polyurethane emulsion, then ultrasonic treatment is carried out to obtain graphene dispersion liquid, the graphene dispersion liquid is added into deionized water for stirring reaction to obtain graphene spraying liquid, the graphene spraying liquid is sprayed onto the surface of the automotive interior leather, and then drying is carried out to obtain the graphene-based antibacterial and wear-resistant automotive interior leather; according to the preparation method, the modified silver-containing graphene is sprayed on the surface of the automobile interior leather, so that the automobile interior leather is endowed with good wear resistance, the automobile interior leather can be effectively protected, the automobile interior leather is prevented from being damaged due to friction and scratch, the service life of the automobile interior leather is prolonged, the modified silver-containing graphene can endow the automobile interior leather with good antibacterial property, bacteria are prevented from breeding and even adhering bacteria are eliminated, the probability of contact between people and bacteria is reduced, and the probability of illness of people is reduced;
in the process of preparing the graphene-based antibacterial and wear-resistant automotive interior leather, firstly, preparing graphene oxide by using graphite powder as a raw material, dispersing the graphene oxide, introducing silver ions on the surface of the graphene oxide, reducing the silver ions to form nano silver to obtain silver-containing graphene, then using triphenylphosphine as a starting material, carrying out metal lithiation to form lithium diphenylphosphine, then reacting with 1, 4-dibromobutane to obtain an intermediate 1, then reacting the intermediate 1 with 3-bromo-1-propanol to form a double quaternary phosphonium group, introducing hydroxyl to obtain an intermediate 2, controlling the use amount of the intermediate 2 and the diphenylmethane diisocyanate to enable one part of the intermediate 2 to react with two parts of the diphenylmethane diisocyanate, introducing two isocyanate groups to obtain an antibacterial connecting agent, modifying the silver-containing graphene through the antibacterial connecting agent, reacting the isocyanate groups on the antibacterial connecting agent with the hydroxyl groups on the silver-containing graphene, and introducing quaternary phosphonium groups and the isocyanate groups on the surface of the silver-containing graphene to obtain the modified silver-containing graphene; the modified silver-containing graphene has the structure that organic matters are connected to the surface of the graphene loaded with nano silver, so that the modified silver-containing graphene is endowed with good dispersibility, and has good mechanical strength, and an antiwear effect is achieved on the surface of the automobile interior leather.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the embodiment is a preparation method of modified silver-containing graphene, which comprises the following steps:
step s1: adding 1g of graphite powder and 0.5g of sodium nitrate into a three-neck flask provided with a stirrer and a thermometer, stirring at the temperature of-5 ℃ at the stirring rate of 400 r/min while adding 20mL of 98% by mass of concentrated sulfuric acid, continuing stirring after the addition for 0.5h, adding 3g of potassium permanganate, continuing stirring for 0.5h, heating to 35 ℃ and continuing stirring for 2h, adding 45mL of deionized water and heating to 90 ℃ and continuing stirring for 2h, pouring the reaction product into 30% by mass of hydrogen peroxide solution after the reaction, standing for precipitation, vacuum filtering, washing a filter cake with 8% by mass of hydrochloric acid solution and distilled water for 3 times sequentially, then placing in a vacuum drying box, and drying for 6h at the temperature of 60 ℃ to obtain graphene oxide;
step s2: adding 0.1g of graphene oxide and 80mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, carrying out ultrasonic treatment for 2 hours under the condition of ultrasonic power of 300W, then adding 20mL of silver nitrate solution with the molar concentration of 0.1 mol/L dropwise under the condition of stirring at the temperature of 25 ℃ and the stirring rate of 400 r/min, controlling the dropping rate to be 1 drop/s, continuing to stir and react for 2 hours after the dropping, adding 3mL of sodium borohydride solution with the mass fraction of 10% dropwise under the condition of stirring, controlling the dropping rate to be 1 drop/s, continuing to stir and react for 5 hours after the dropping, centrifuging a reaction product after the dropping, washing a precipitate with distilled water for 3 hours, and then placing the precipitate in a vacuum drying box and drying for 3 hours under the condition of 60 ℃ to obtain the silver-containing graphene;
step s3: adding 0.1mol of triphenylphosphine, 0.8g of potassium tert-butoxide, 0.2mol of lithium and 80mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring at a temperature of-5 ℃ and a stirring rate of 400 r/min for reaction for 20min, heating to 35 ℃ for continuous stirring for reaction for 8h, cooling to-5 ℃ for continuous stirring for reaction for 0.11 mol of ammonium chloride, heating to 10 ℃ for continuous stirring for reaction for 2h, dropwise adding 0.05mol of 1, 4-dibromobutane while stirring, controlling the dropwise adding rate to be 1 drop/s, continuously stirring for reaction for 5h after the dropwise adding, cooling the reaction product to room temperature after the reaction is finished, rotationally evaporating to remove the solvent, sequentially washing with 8% hydrochloric acid solution, distilled water and absolute methanol for 2 times, and then recrystallizing with chloroform to obtain an intermediate 1;
step s4: adding 0.1mol of intermediate 1, 0.22mol of 3-bromo-1-propanol and 120mL of chloroform into a three-neck flask provided with a thermometer, a stirrer and an air duct, introducing nitrogen for protection, stirring and reacting for 15 min under the conditions of 25 ℃ and 400 r/min of stirring rate, then heating to 60 ℃ and continuing stirring and reacting for 40h, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, and then recrystallizing with ethyl acetate to obtain an intermediate 2;
step s5: adding 10mmo l of intermediate 2, 20mmo l of diphenylmethane diisocyanate, 0.1g of dibutyltin dilaurate and 40mL of dichloromethane into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 0.5h under the condition that the temperature is 25 ℃ and the stirring rate is 400 r/min, heating to reflux, continuing stirring and reacting for 6h, cooling the reaction product to room temperature after the reaction is finished, rotationally evaporating to remove the solvent, and recrystallizing with ethyl acetate to obtain an antibacterial connecting agent;
step s6: adding 1g of silver-containing graphene, 120mLN and N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, performing ultrasonic treatment for 2 hours under the condition of ultrasonic power of 300W, adding 0.5g of an antibacterial connecting agent and 0.005g of dibutyltin dilaurate, continuing ultrasonic treatment for 5 min, introducing nitrogen for protection, stirring at the temperature of 25 ℃ and the stirring rate of 400 r/min for reacting for 0.5 hours, heating to reflux for continuing stirring for reacting for 8 hours, cooling the reaction product to room temperature after the reaction is finished, centrifuging, washing the precipitate with methylene dichloride for 3 times, and then placing in a vacuum drying oven, and drying at the temperature of 40 ℃ for 10 hours to obtain the modified silver-containing graphene.
Example 2:
the embodiment is a preparation method of modified silver-containing graphene, which comprises the following steps:
step s1: adding 1g of graphite powder and 0.8g of sodium nitrate into a three-neck flask provided with a stirrer and a thermometer, stirring at a temperature of 0 ℃ and a stirring rate of 500r/min, adding 25mL of 98% by mass of concentrated sulfuric acid, continuing stirring for reaction for 1h after the addition, adding 4g of potassium permanganate, continuing stirring for reaction for 1h, heating to 40 ℃ and continuing stirring for reaction for 3h, adding 50mL of deionized water and heating to 95 ℃, continuing stirring for reaction for 3h, pouring a reaction product into 30% by mass of hydrogen peroxide solution after the reaction, standing for precipitation, vacuum filtering, washing a filter cake with 10% by mass of hydrochloric acid solution and distilled water for 5 times sequentially, then placing in a vacuum drying box, and drying for 8h at a temperature of 65 ℃ to obtain graphene oxide;
step s2: adding 0.1g of graphene oxide and 100mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, carrying out ultrasonic treatment for 3h under the condition of ultrasonic power of 350W, then adding 30mL of silver nitrate solution with the molar concentration of 0.2mol/L dropwise under the condition of the temperature of 30 ℃ and the stirring rate of 500r/min, controlling the dropping rate to be 2 drops/s, continuing to stir and react for 2.5h after the dropping, adding 5mL of sodium borohydride solution with the mass fraction of 12% dropwise under the condition of stirring, controlling the dropping rate to be 2 drops/s, continuing to stir and react for 6h after the dropping, centrifuging a reaction product after the dropping, washing a precipitate with distilled water for 5 times, then placing the precipitate in a vacuum drying box, and drying for 5h under the condition of the temperature of 65 ℃ to obtain the silver-containing graphene;
step s3: adding 0.1mol of triphenylphosphine, 1.2g of potassium tert-butoxide, 0.22mol of lithium and 100mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 30 min at the temperature of 0 ℃ and the stirring rate of 500r/min, continuously stirring and reacting for 10h at the temperature of 40 ℃, then adding 0.13mol of ammonium chloride at the temperature of 0 ℃ and continuously stirring and reacting for 3h, then adding 0.05mol of 1, 4-dibromobutane dropwise while stirring at the temperature of 15 ℃, controlling the dropping rate to be 2 drops/s, continuously stirring and reacting for 6h after the dropping, cooling the reaction product to room temperature after the reaction, rotationally evaporating and removing the solvent, sequentially washing for 3 times with hydrochloric acid solution with the mass fraction of 10%, distilled water and anhydrous methanol, and then recrystallizing with chloroform to obtain an intermediate 1;
step s4: adding 0.1mol of intermediate 1, 0.25mol of 3-bromo-1-propanol and 150mL of chloroform into a three-neck flask provided with a thermometer, a stirrer and an air duct, introducing nitrogen for protection, stirring and reacting for 20min under the condition that the temperature is 30 ℃ and the stirring rate is 500r/min, then heating to 65 ℃ and continuing stirring and reacting for 50h, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, and then recrystallizing with ethyl acetate to obtain an intermediate 2;
step s5: adding 10mmo l of intermediate 2, 20mmo l of diphenylmethane diisocyanate, 0.15g of dibutyltin dilaurate and 50mL of dichloromethane into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 1h under the condition that the temperature is 30 ℃ and the stirring rate is 500r/min, heating to reflux, continuing stirring and reacting for 8h, cooling the reaction product to room temperature after the reaction is finished, rotationally evaporating to remove the solvent, and recrystallizing with ethyl acetate to obtain an antibacterial connecting agent;
step s6: 1g of silver-containing graphene, 150mLN and N-dimethylformamide are added into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, ultrasonic treatment is carried out for 3 hours under the condition that ultrasonic power is 350W, then 1.5g of antibacterial connecting agent and 0.01g of dibutyltin dilaurate are added for continuous ultrasonic treatment for 10 min, then nitrogen protection is introduced, stirring reaction is carried out for 1 hour under the condition that the temperature is 30 ℃ and the stirring speed is 500r/min, then stirring reaction is carried out for 10 hours under the condition that the temperature is increased to reflux, after the reaction is finished, the reaction product is cooled to room temperature, then centrifugation is carried out, precipitate is washed for 5 times by methylene dichloride, and then the precipitate is placed into a vacuum drying oven and dried for 15 hours under the condition that the temperature is 45 ℃ to obtain the modified silver-containing graphene.
Example 3:
the embodiment relates to a preparation method of graphene-based antibacterial and wear-resistant automotive interior leather, which comprises the following steps:
step one: weighing 2 parts of modified silver-containing graphene, 20 parts of polyurethane emulsion and 55 parts of deionized water according to parts by weight for later use; the modified silver-containing graphene is the modified silver-containing graphene in example 1; the polyurethane emulsion is aqueous polyurethane emulsion PU-402, and the solid content is 50%;
step two: adding modified silver-containing graphene into polyurethane emulsion, and then carrying out ultrasonic treatment on the polyurethane emulsion under the condition that the ultrasonic power is 300W for 15 min to obtain graphene dispersion liquid;
step three: adding the graphene dispersion liquid into deionized water, and stirring and reacting for 0.5h under the conditions that the temperature is 35 ℃ and the stirring rate is 400 r/min to obtain graphene spraying liquid;
step four: and (3) spraying the graphene spraying liquid onto the surface of the automobile interior leather, wherein the spraying amount is 10g/sf, and drying to obtain the graphene-based antibacterial and wear-resistant automobile interior leather.
Example 4:
the embodiment relates to a preparation method of graphene-based antibacterial and wear-resistant automotive interior leather, which comprises the following steps:
step one: weighing 12 parts of modified silver-containing graphene, 25 parts of polyurethane emulsion and 65 parts of deionized water according to parts by weight for later use; the modified silver-containing graphene is the modified silver-containing graphene in example 2; the polyurethane emulsion is aqueous polyurethane emulsion PU-402, and the solid content is 50%;
step two: adding modified silver-containing graphene into polyurethane emulsion, and performing ultrasonic treatment on the polyurethane emulsion under the condition that the ultrasonic power is 350W for 20min to obtain graphene dispersion liquid;
step three: adding the graphene dispersion liquid into deionized water, and stirring and reacting for 1h under the conditions that the temperature is 45 ℃ and the stirring rate is 500r/min to obtain graphene spraying liquid;
step four: and (3) spraying the graphene spraying liquid onto the surface of the automobile interior leather, wherein the spraying amount is 15g/sf, and drying to obtain the graphene-based antibacterial and wear-resistant automobile interior leather.
Comparative example 1:
comparative example 1 differs from example 4 in that modified silver-containing graphene was not added.
Comparative example 2:
comparative example 2 is different from example 4 in that graphene oxide is added instead of modified silver-containing graphene.
Comparative example 3:
comparative example 3 is different from example 4 in that silver-containing graphene is added instead of modified silver-containing graphene.
The properties of graphene-based antibacterial and abrasion-resistant automotive interior leather of examples 3 to 4 and comparative examples 1 to 3 were tested, the antibacterial test bacteria were staphylococcus aureus and bacillus subtilis, the abrasion resistance was measured with reference to QB/T2726-2005 "determination of abrasion resistance for leather physical and mechanical test", and the test results are shown below:
| sample of | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Antibacterial rate of staphylococcus aureus,% | 98.5 | 99.9 | 53.8 | 76.4 | 90.3 |
| Antibacterial rate of bacillus subtilis% | 97.9 | 99.1 | 50.6 | 75.2 | 88.0 |
| Wear resistance grade, grade | 4 | 4 | 3 | 4 | 4 |
Referring to the above table data, according to the comparison of examples 3-4 and comparative examples 1-3, it can be known that the addition of graphene oxide, silver-containing graphene and modified silver-containing graphene can improve the wear resistance of the automotive interior leather, and the addition of silver-containing graphene and modified silver-containing graphene can also greatly improve the antibacterial property of the automotive interior leather, wherein the comprehensive improvement effect of the modified silver-containing graphene is better.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. The preparation method of the graphene-based antibacterial wear-resistant automotive interior leather is characterized by comprising the following steps of:
step one: weighing 2-12 parts of modified silver-containing graphene, 20-25 parts of polyurethane emulsion and 55-65 parts of deionized water according to parts by weight for standby;
step two: adding modified silver-containing graphene into polyurethane emulsion, and performing ultrasonic treatment for 15-20min under the condition that the ultrasonic power is 300-350W to obtain graphene dispersion liquid;
step three: adding the graphene dispersion liquid into deionized water, and then stirring and reacting for 0.5-1h under the conditions that the temperature is 35-45 ℃ and the stirring speed is 400-500r/min to obtain graphene spraying liquid;
step four: spraying graphene spraying liquid onto the surface of the automobile interior leather, wherein the spraying amount is 10-15g/sf, and drying to obtain the graphene-based antibacterial and wear-resistant automobile interior leather;
the modified silver-containing graphene is prepared by the following steps:
step s1: adding graphite powder and sodium nitrate into a three-neck flask, adding concentrated sulfuric acid while stirring, sequentially adding potassium permanganate and deionized water, continuously stirring for reaction, pouring a reaction product into a hydrogen peroxide solution after the reaction is finished, standing for precipitation, vacuum filtering, washing a filter cake, and drying to obtain graphene oxide;
step s2: adding graphene oxide and deionized water into a three-neck flask for ultrasonic treatment, then dropwise adding a silver nitrate solution while stirring, continuing stirring for reaction after dropwise adding, then dropwise adding a sodium borohydride solution while stirring, continuing stirring for reaction after dropwise adding, centrifuging a reaction product after the reaction is finished, washing and drying a precipitate to obtain silver-containing graphene;
step s3: adding triphenylphosphine, potassium tert-butoxide, lithium and tetrahydrofuran into a three-neck flask, stirring for reaction, adding ammonium chloride, continuously stirring for reaction, dropwise adding 1, 4-dibromobutane while stirring, continuously stirring for reaction after the dropwise adding is finished, cooling a reaction product after the reaction is finished, performing rotary evaporation, washing, and recrystallizing to obtain an intermediate 1;
step s4: adding the intermediate 1, 3-bromo-1-propanol and chloroform into a three-neck flask, stirring for reaction, cooling a reaction product after the reaction is finished, and performing rotary evaporation and recrystallization to obtain an intermediate 2;
step s5: adding the intermediate 2, diphenylmethane diisocyanate, dibutyltin dilaurate and methylene dichloride into a three-neck flask, stirring for reaction, cooling a reaction product after the reaction is finished, and performing rotary evaporation and recrystallization to obtain an antibacterial connecting agent;
step s6: adding silver-containing graphene and N, N-dimethylformamide into a three-neck flask for ultrasonic treatment, then adding an antibacterial connecting agent and dibutyltin dilaurate for continuous ultrasonic treatment, stirring for reaction, cooling a reaction product after the reaction is finished, centrifuging, washing and drying a precipitate, and obtaining the modified silver-containing graphene.
2. The preparation method of the graphene-based antibacterial wear-resistant automotive interior leather is characterized in that the polyurethane emulsion is aqueous polyurethane emulsion PU-402 and has a solid content of 50%.
3. The method for preparing the graphene-based antibacterial and wear-resistant automotive interior leather according to claim 1, wherein the dosage ratio of the graphite powder to the sodium nitrate to the concentrated sulfuric acid to the potassium permanganate to the deionized water in the step s1 is 1g:0.5-0.8g:20-25mL:3-4g:45-50mL, wherein the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the hydrogen peroxide solution is 30%.
4. The method for preparing the graphene-based antibacterial and wear-resistant automotive interior leather according to claim 1, wherein the dosage ratio of the graphene oxide, deionized water, silver nitrate solution and sodium borohydride solution in the step s2 is 0.1g:80-100mL:20-30mL:3-5mL, wherein the molar concentration of the silver nitrate solution is 0.1-0.2mol/L, and the mass fraction of the sodium borohydride solution is 10-12%.
5. The method for preparing the graphene-based antibacterial and wear-resistant automotive interior leather according to claim 1, wherein the dosage ratio of triphenylphosphine, potassium tert-butoxide, lithium, tetrahydrofuran, ammonium chloride and 1, 4-dibromobutane in the step s3 is 0.1mol:0.8-1.2g:0.2 to 0.22mol:80-100mL:0.11-0.13mol:0.05mol, wherein the mass fraction of the hydrochloric acid solution is 8-10%.
6. The method for preparing the graphene-based antibacterial and wear-resistant automotive interior leather according to claim 1, wherein the dosage ratio of the intermediate 1, 3-bromo-1-propanol and chloroform in the step s4 is 0.1mol:0.22 to 0.25mol:120-150mL.
7. The method for preparing the graphene-based antibacterial and wear-resistant automotive interior leather according to claim 1, wherein the dosage ratio of the intermediate 2, diphenylmethane diisocyanate, dibutyltin dilaurate and methylene dichloride in the step s5 is 10mmol:20mmol:0.1-0.15g:40-50mL.
8. The method for preparing the graphene-based antibacterial and wear-resistant automotive interior leather according to claim 1, wherein the dosage ratio of the silver-containing graphene to the N, N-dimethylformamide to the antibacterial connecting agent to the dibutyltin dilaurate in the step s6 is 1g:120-150mL:0.5-1.5g:0.005-0.01g.
9. The graphene-based antibacterial and wear-resistant automotive interior leather is characterized in that the graphene-based antibacterial and wear-resistant automotive interior leather is prepared by the preparation method of the graphene-based antibacterial and wear-resistant automotive interior leather according to any one of claims 1-8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117701787A (en) * | 2024-02-02 | 2024-03-15 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
| CN117701787B (en) * | 2024-02-02 | 2024-05-03 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016011905A1 (en) * | 2014-07-25 | 2016-01-28 | 中国科学院深圳先进技术研究院 | Silver-doped graphene composite paper and preparation method therefor |
| CN105772739A (en) * | 2016-03-12 | 2016-07-20 | 常州大学 | Preparation method for graphene/nano-silver composite antibacterial material |
| CN106337316A (en) * | 2016-08-29 | 2017-01-18 | 佛山市高明区尚润盈科技有限公司 | Method for preparing antibacterial and anti-radiation corrugated paperboard |
| US20190126211A1 (en) * | 2017-10-27 | 2019-05-02 | Soochow University | Titanium dioxide / sulfonated graphene oxide / ag nanoparticle composite membrane and preparation and application thereof |
| CN110041497A (en) * | 2019-05-15 | 2019-07-23 | 安徽大学 | Carry silver-colored graphene/waterborne polyurethane-acrylate antimicrobial emulsion and preparation method thereof |
-
2023
- 2023-07-05 CN CN202310816076.0A patent/CN116814146A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016011905A1 (en) * | 2014-07-25 | 2016-01-28 | 中国科学院深圳先进技术研究院 | Silver-doped graphene composite paper and preparation method therefor |
| CN105772739A (en) * | 2016-03-12 | 2016-07-20 | 常州大学 | Preparation method for graphene/nano-silver composite antibacterial material |
| CN106337316A (en) * | 2016-08-29 | 2017-01-18 | 佛山市高明区尚润盈科技有限公司 | Method for preparing antibacterial and anti-radiation corrugated paperboard |
| US20190126211A1 (en) * | 2017-10-27 | 2019-05-02 | Soochow University | Titanium dioxide / sulfonated graphene oxide / ag nanoparticle composite membrane and preparation and application thereof |
| CN110041497A (en) * | 2019-05-15 | 2019-07-23 | 安徽大学 | Carry silver-colored graphene/waterborne polyurethane-acrylate antimicrobial emulsion and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117701787A (en) * | 2024-02-02 | 2024-03-15 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
| CN117701787B (en) * | 2024-02-02 | 2024-05-03 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
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