CN117866373A - Antibacterial composite material for air conditioner and preparation method thereof - Google Patents
Antibacterial composite material for air conditioner and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 79
- 239000002245 particle Substances 0.000 claims abstract description 51
- 229920001690 polydopamine Polymers 0.000 claims abstract description 47
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 34
- 239000011032 tourmaline Substances 0.000 claims abstract description 33
- 229940070527 tourmaline Drugs 0.000 claims abstract description 33
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 15
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 15
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 15
- 239000010432 diamond Substances 0.000 claims abstract description 14
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000000806 elastomer Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 claims description 80
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 76
- 238000001035 drying Methods 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 39
- 239000011787 zinc oxide Substances 0.000 claims description 38
- TUFYVOCKVJOUIR-UHFFFAOYSA-N alpha-Thujaplicin Natural products CC(C)C=1C=CC=CC(=O)C=1O TUFYVOCKVJOUIR-UHFFFAOYSA-N 0.000 claims description 32
- 229930007845 β-thujaplicin Natural products 0.000 claims description 32
- 238000009210 therapy by ultrasound Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 26
- 238000007873 sieving Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- -1 phospholanthanum cerium Chemical compound 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229960002233 benzalkonium bromide Drugs 0.000 claims description 10
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 10
- VBGGLSWSRVDWHB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBGGLSWSRVDWHB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
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- 230000000052 comparative effect Effects 0.000 description 9
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- 241000282414 Homo sapiens Species 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an antibacterial composite material for an air conditioner and a preparation method thereof, and belongs to the technical field of antibacterial materials. Is prepared from TPE elastomer (28-40-wt%), magnesium silicate (15-25-wt%), tourmaline powder mixture (2-5-wt%), diamond powder (0.4-0.6-wt%), activated carbon (5-8-wt%), nano-titanium dioxide particles modified by silane (5-8-wt%), polydopamine antibacterial agent (1-4-wt%), surfactant (1-5-wt%) and deionized water (30-40-wt%). The composite material prepared by the invention has good antibacterial property, can realize the antibacterial property of an air outlet pipeline of an air conditioner, and simultaneously releases anions to improve the concentration of the anions in the air.
Description
Technical Field
The invention belongs to the technical field of antibacterial materials, and relates to an antibacterial composite material for an air conditioner and a preparation method thereof.
Background
Nowadays, air conditioners are increasingly applied to the life of human beings, the use frequency is also higher, and the life of people is more and more independent of the air conditioners. As an important part of indoor environment, the air conditioner is easy to generate harmful substances such as bacteria, viruses and the like if not subjected to cleaning and disinfection treatment, and has an important threat to human health.
In the long-term use process of the air conditioner, the air outlet pipe is easy to adhere dust and bacteria; and after the refrigerating or heating function is started, the inner wall of the air outlet channel is wet due to the condensing function, so that a large amount of bacteria and mold are easy to breed. The harmful bacteria can blow into the room after the air conditioner is started and the air is discharged, so that the indoor air pollution is aggravated, the air quality is deteriorated, and the health is damaged.
When the air conditioner is not in use, dust, bacteria and mildew are easily accumulated. Once the use is restarted, the viruses and microorganisms are blown out from the air outlet, so that fresh air in a room is polluted, and various hazards are easily caused.
The antibacterial method of the air conditioner commonly used at present is to place an antibacterial dust screen at an air conditioner return air inlet to play a role in filtering and resisting bacteria, and most of traditional antibacterial dust screens are prepared by adding antibacterial agents into materials, so that the materials can have better antibacterial performance. Traditional antibacterial agents, such as silver ion antibacterial agents, but the dosage of the silver ion antibacterial agents has great influence on the performance of materials, such as poor toughness, poor molding and reduced hardness of the materials; and too small a dose does not achieve good antibacterial properties. Polydopamine has abundant chemical properties and unique photo-thermal, antioxidation, adhesion and biocompatibility, and is widely applied to the field of composite antibacterial materials. The polydopamine can be used as an optimized material to be combined with other antibacterial agents, so that better antibacterial capability can be obtained.
There is therefore a need to develop a new antibacterial material to solve the above problems.
Disclosure of Invention
The invention aims to provide an antibacterial composite material for an air conditioner and a preparation method thereof, and the prepared antibacterial composite material can perform antibacterial treatment on an air outlet pipeline, simultaneously release anions and radiate far infrared rays, improve the concentration of anions in the air and improve the air quality.
The aim of the invention can be achieved by the following technical scheme:
an antibacterial composite material for an air conditioner comprises the following components in percentage by mass:
28-40% of TPE elastomer, 15-25% wt% of magnesium silicate, 2-5% of tourmaline powder mixture, 0.4-0.6 wt% of diamond powder, 5-8 wt% of activated carbon, 5-8 wt% of nano titanium dioxide particles modified by silane, 1-4% of polydopamine antibacterial agent, 1-5 wt% of surfactant and 30-40% wt% of deionized water;
the preparation of the polydopamine antibacterial agent is as follows:
s1, mixing a dopamine hydrochloride solution with the mass concentration of 0.05 g/ml and a sodium carbonate solution with the mass concentration of 30% in a volume ratio of 1:1, heating in a water bath at 55 ℃ for reaction for 10-12 h, centrifuging the obtained reaction solution, washing with methanol, and drying in a constant temperature oven at 100 ℃ for 2 h to obtain polydopamine solid;
s2, drying the nano zinc oxide with the particle size of 50-100 nm in a baking oven to 18-24 h at the temperature of 80-100 ℃, fully mixing the dried nano zinc oxide with absolute ethyl alcohol, performing ultrasonic treatment on the tip for 20-30 min, adding a silane coupling agent KH560 with the mass concentration of 5% and the mass concentration of 10% of the nano zinc oxide to perform surface treatment, stirring and reacting for 4-5 h under the water bath heating condition of 80 ℃, filtering, washing filter residues with absolute ethyl alcohol for 2-3 times, drying in the baking oven at the temperature of 100 ℃ for 12-24 h, grinding with a ball mill at the rotating speed of 700-1000 r/min, and sieving for 100-400 meshes for standby to obtain modified nano zinc oxide;
s3, fully crushing hinokitiol solid, sieving with a 200-mesh sieve to obtain hinokitiol powder, adding benzalkonium bromide and absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture to obtain 0.5h so as to uniformly disperse the hinokitiol powder and obtain modified hinokitiol;
s4, adding polydopamine solid, modified nano zinc oxide, a surfactant and absolute ethyl alcohol into the modified hinokitiol, carrying out ultrasonic treatment on the mixed solution for 0.5-h until the mixed solution is completely and uniformly mixed, then carrying out microwave treatment for 15-25 min, filtering, and drying in a constant temperature oven at 100 ℃ for 2-h to obtain the polydopamine antibacterial agent, wherein the microwave treatment power is 100-200W.
As a preferable technical scheme of the invention, the grain size of the tourmaline powder mixture is 1500-2000 meshes, the grain size of the diamond powder is 1000-1500 meshes, and the grain size of the magnesium silicate is 3000-4000 meshes after being ground by a grinder.
As a preferable technical scheme of the invention, the surfactant in the antibacterial composite material component for the air conditioner is one or more of castor oil, polyethylene glycol and carboxymethyl cellulose.
As a preferable technical scheme of the invention, the tourmaline powder mixture is a mixture of tourmaline powder and phospholanthanum cerium powder, and the mass ratio of the tourmaline powder to the phospholanthanum cerium powder is 8:2.
As a preferable technical scheme of the invention, in the step S3, the composition ratio of the hinokitiol, the benzalkonium bromide and the absolute ethyl alcohol is 30-50 wt percent: 1-5 wt%: 30-50 wt%.
In step S4, as a preferred technical scheme of the present invention, the composition ratio of the modified hinokitiol, polydopamine solid, modified nano zinc oxide, surfactant, and absolute ethanol is 10-15 wt%: 30-50 wt%: 2-10 wt%: 1-4 wt%: 20-50% wt%.
In a preferred embodiment of the present invention, in step S4, the surfactant is one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
As a preferable technical scheme of the invention, the specific preparation process of the nano titanium dioxide particles modified by silane is as follows:
drying nano titanium dioxide in an oven at 100-120 ℃, adding perfluorodecyl trimethoxy silane into absolute ethyl alcohol, fully stirring and carrying out ultrasonic treatment to obtain silane solution; adding the high-temperature dried nano titanium dioxide into a silane solution, fully and uniformly stirring, and then carrying out centrifugal filtration, washing and drying 2 h to obtain nano titanium dioxide particles modified by silane; wherein the composition ratio of the dried nano titanium dioxide, the perfluorodecyl trimethoxy silane and the absolute ethyl alcohol is 36-45 wt percent: 1-4 wt%: 40-65 wt percent.
The specific preparation method of the antibacterial composite material for the air conditioner comprises the following steps:
grinding TPE elastomer, magnesium silicate, tourmaline powder mixture, diamond powder, activated carbon and nano titanium dioxide particles modified by silane by a ball mill according to mass percent, wherein the rotating speed is 900-1100 r/min, and the time is 1-2 h, so that the components are fully mixed;
fully dispersing fully mixed solid powder in deionized water by ultrasonic treatment of 0.5-1 h, adding a polydopamine antibacterial agent and a surfactant, fully stirring uniformly in a stirrer, reacting for 5-15 min by a microwave method, wherein the microwave treatment power is 200-300W, drying the obtained product in an oven at the drying temperature of 95-100 ℃, mechanically granulating and sieving the dried solid by a production line to obtain the antibacterial composite material for the air conditioner.
The invention has the beneficial effects that:
(1) Hinokitiol is a natural antibacterial agent, has good antibacterial property, is treated by adding a surfactant, is uniformly dispersed, and meanwhile, the benzalkonium bromide has antibacterial property, so that the antibacterial property of hinokitiol is further improved; the polydopamine and the hinokitiol antibacterial agent are combined, so that the nano zinc oxide and the hinokitiol antibacterial solution are uniformly dispersed in the polydopamine, and better antibacterial capability is obtained.
(2) Tourmaline powder mixture and magnesium silicate are added into the composite material, so that anions can be released, the anions have antibacterial function, the antibacterial effect can be further enhanced, and meanwhile, the concentration of the anions in the air is improved; by adding the activated carbon, the porous structure of the activated carbon can be utilized, so that the specific surface area of the material is increased, and peculiar smell can be adsorbed at the same time; the addition of the nano titanium dioxide treated by silane strengthens the hydrophobicity of the material, prevents mildew caused by too high humidity, also avoids the agglomeration of the nano titanium dioxide, and does not influence the release function of negative ions of the material.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
The TPE elastomer in the following examples and comparative examples is a styrenic TPE (SBS), manufacturer is micin, product No.: p886285, the remaining raw materials are all from national pharmaceutical group chemical reagent Co.
Example 1
Preparing a polydopamine antibacterial agent:
s1, mixing a dopamine hydrochloride solution with the mass concentration of 0.05 g/ml and a sodium carbonate solution with the mass concentration of 30% in a volume ratio of 1:1, heating in a water bath at 55 ℃ to react for 12: 12 h, centrifuging the obtained reaction solution, washing with methanol, and drying in a constant temperature oven at 100 ℃ for 2: 2 h to obtain polydopamine solid;
s2, drying nano zinc oxide with the particle size of 50 nm in a baking oven for 20 h at the temperature of 100 ℃, fully mixing the dried nano zinc oxide with absolute ethyl alcohol, performing ultrasonic treatment on the tip for 20 min, adding KH560 with the mass concentration of 5% and the mass percentage of 10% of the nano zinc oxide for surface treatment, stirring for reaction for 4h under the water bath heating condition of 80 ℃, filtering, washing filter residues with absolute ethyl alcohol for 2 times, drying for 18 h at the temperature of 100 ℃ in the baking oven, grinding with a ball mill, sieving for 100 meshes for standby, and obtaining modified nano zinc oxide;
s3, fully crushing hinokitiol solid, sieving with a 200-mesh sieve to obtain hinokitiol powder, adding 4-wt% of benzalkonium bromide and 50-wt% of absolute ethyl alcohol into 46-wt% of hinokitiol, and carrying out ultrasonic treatment to uniformly disperse the hinokitiol powder to obtain modified hinokitiol;
s4, adding 40. wt% of polydopamine solid, 10. wt% of modified nano zinc oxide, 3. wt% of sodium dodecyl sulfate and 37. wt% of absolute ethyl alcohol into 10. wt% of modified hinokitiol, carrying out ultrasonic treatment on the mixed solution until the mixed solution is completely and uniformly mixed, carrying out microwave treatment for 15 min with the power of 100. W, filtering, and drying 2. h in a 100 ℃ incubator to obtain the polydopamine antibacterial agent.
Preparing silane modified nano titanium dioxide particles:
drying nano titanium dioxide in a drying oven at 100 ℃, adding 4 percent wt percent of perfluoro decyl trimethoxy silane and 36 percent wt percent of dried nano titanium dioxide into 60 percent wt percent absolute ethyl alcohol, fully and uniformly stirring, and then carrying out centrifugal filtration, washing and drying for 2 h to obtain nano titanium dioxide particles modified by silane.
Preparing an antibacterial composite material for an air conditioner:
30. 30 wt percent of TPE elastomer, 15. 15 wt percent of magnesium silicate with the particle size of 3000 meshes, 5.5 wt percent of tourmaline powder mixture, 0.5. 0.5 wt percent of diamond powder with the particle size of 1000 meshes, 5.5 wt percent of activated carbon and 6. 6 wt percent of nano titanium dioxide particles modified by silane are ground by a ball mill to 1.5 h with the rotating speed of 1000 r/min, wherein the mass ratio of the tourmaline powder mixture is 8:2 tourmaline powder and phospholanthanum cerium powder;
fully dispersing fully mixed solid powder in 30 wt% deionized water after ultrasonic treatment for 0.5h, adding 4 wt% polydopamine antibacterial agent and 4 wt% castor oil, fully stirring uniformly in a stirrer, reacting for 10 min by using microwaves with the power of 200W, drying the obtained product in an oven for 3 h, drying at 95 ℃, mechanically granulating and sieving the dried solid through a production line to obtain the antibacterial composite material for the air conditioner.
Example 2
Preparing a polydopamine antibacterial agent:
s1, mixing a dopamine hydrochloride solution with the mass concentration of 0.05 g/ml and a sodium carbonate solution with the mass concentration of 30% in a volume ratio of 1:1, heating in a water bath at 55 ℃ to react for 12: 12 h, centrifuging the obtained reaction solution, washing with methanol, and drying in a constant temperature oven at 100 ℃ for 2: 2 h to obtain polydopamine solid;
s2, drying nano zinc oxide with the particle size of 100 nm in a baking oven for 20 h at the temperature of 100 ℃, fully mixing the dried nano zinc oxide with absolute ethyl alcohol, performing ultrasonic treatment on the tip for 20 min, adding KH560 with the mass concentration of 5% and the mass percentage of 10% of the nano zinc oxide for surface treatment, stirring for reaction for 4h under the water bath heating condition of 80 ℃, filtering, washing filter residues with absolute ethyl alcohol for 2 times, drying for 18 h at the temperature of 100 ℃ in the baking oven, grinding with a ball mill, sieving for 200 meshes for later use, and obtaining modified nano zinc oxide;
s3, fully crushing hinokitiol solid, sieving with a 200-mesh sieve to obtain hinokitiol powder, adding 4-wt% of benzalkonium bromide and 50-wt% of absolute ethyl alcohol into 46-wt% of hinokitiol, and carrying out ultrasonic treatment to uniformly disperse the hinokitiol powder to obtain modified hinokitiol;
s4, adding 40. wt% of polydopamine solid, 10. wt% of modified nano zinc oxide, 3. wt% of sodium dodecyl sulfate and 37. wt% of absolute ethyl alcohol into 10. wt% of modified hinokitiol, carrying out ultrasonic treatment on the mixed solution until the mixed solution is completely and uniformly mixed, carrying out microwave treatment for 15 min with the power of 100. W, filtering, and drying 2. h in a 100 ℃ incubator to obtain the polydopamine antibacterial agent.
Preparing silane modified nano titanium dioxide particles:
at 120 ℃, the nano titanium dioxide is dried in a baking oven, 4 percent wt percent of perfluoro decyl trimethoxy silane and 40 percent wt percent of dried nano titanium dioxide are added into 56 percent wt percent absolute ethyl alcohol, and the mixture is fully and uniformly stirred, and then the mixture is centrifugally filtered, washed and dried for 2 h to obtain nano titanium dioxide particles modified by silane.
Preparing an antibacterial composite material for an air conditioner:
30. wt percent of TPE elastomer, 15. wt percent of magnesium silicate with the particle size of 3500 meshes, 5. wt percent of tourmaline powder mixture, 0.5. wt percent of diamond powder with the particle size of 1200 meshes, 6. wt percent of activated carbon and 5. wt percent of nano titanium dioxide particles modified by silane are ground by a ball mill according to the mass parts, the rotating speed is 1000. r/min, wherein the mass ratio of the tourmaline powder mixture is 8:2 tourmaline powder and phospholanthanum cerium powder;
fully dispersing fully mixed solid powder in 30 wt% deionized water after ultrasonic treatment for 0.5h, adding 3.5 wt% polydopamine antibacterial agent and 5 wt% carboxymethyl cellulose, fully and uniformly stirring in a stirrer, reacting for 10 min by using microwaves with the power of 200W, drying the obtained product in an oven at 4h and the drying temperature of 100 ℃, and mechanically granulating and sieving the dried solid through a production line to obtain the antibacterial composite material for the air conditioner.
Example 3
Preparing a polydopamine antibacterial agent:
s1, mixing a dopamine hydrochloride solution with the mass concentration of 0.05 g/ml and a sodium carbonate solution with the mass concentration of 30% in a volume ratio of 1:1, heating in a water bath at 55 ℃ to react for 12: 12 h, centrifuging the obtained reaction solution, washing with methanol, and drying in a constant temperature oven at 100 ℃ for 2: 2 h to obtain polydopamine solid;
s2, drying nano zinc oxide with the particle size of 80 nm in a baking oven to 20 h at the temperature of 100 ℃, fully mixing the dried nano zinc oxide with absolute ethyl alcohol, performing ultrasonic treatment on the tip for 20 min, adding KH560 with the mass concentration of 5% and the mass percentage of 10% of the nano zinc oxide for surface treatment, stirring and reacting for 4h under the water bath heating condition of 80 ℃, filtering, washing filter residues with absolute ethyl alcohol for 2 times, drying in the baking oven at the temperature of 100 ℃ to 18 h, grinding with a ball mill at the rotating speed of 800 r/min, and sieving for 400 meshes for later use to obtain modified nano zinc oxide;
s3, fully crushing hinokitiol solid, sieving with a 200-mesh sieve to obtain hinokitiol powder, adding 4-wt% of benzalkonium bromide and 50-wt% of absolute ethyl alcohol into 46-wt% of hinokitiol, and carrying out ultrasonic treatment to uniformly disperse the hinokitiol powder to obtain modified hinokitiol;
s4, adding 40. wt% of polydopamine solid, 10. wt% of modified nano zinc oxide, 3. wt% of sodium dodecyl sulfate and 37. wt% of absolute ethyl alcohol into 10. wt% of modified hinokitiol, carrying out ultrasonic treatment on the mixed solution until the mixed solution is completely and uniformly mixed, carrying out microwave treatment for 15 min with the power of 200. W, filtering, and drying 2. h in a 100 ℃ incubator to obtain the polydopamine antibacterial agent.
Preparing silane modified nano titanium dioxide particles:
at 110 ℃, the nano titanium dioxide is dried in a baking oven, 4 percent wt percent of perfluoro decyl trimethoxy silane and 45 percent wt percent of dried nano titanium dioxide are added into 51 percent wt percent absolute ethyl alcohol, and the mixture is fully and uniformly stirred, and then the mixture is centrifugally filtered, washed and dried for 2 h to obtain nano titanium dioxide particles modified by silane.
Preparing an antibacterial composite material for an air conditioner:
28. wt% of TPE elastomer, 15. wt% of magnesium silicate with the particle size of 4000 meshes, 4. wt% of tourmaline powder mixture, 0.5. wt% of diamond powder with the particle size of 1500 meshes, 6. wt% of activated carbon and 8. wt% of nano titanium dioxide particles modified by silane are ground by a ball mill according to the mass parts, the rotating speed is 1000 r/min, wherein the mass ratio of the tourmaline powder mixture is 8:2 tourmaline powder and phospholanthanum cerium powder;
fully dispersing fully mixed solid powder in 30 wt% deionized water after ultrasonic treatment for 0.5h, adding 4. 4 wt% polydopamine antibacterial agent and 4.5 wt% carboxymethyl cellulose, fully and uniformly stirring in a stirrer, reacting for 12 min by using microwaves with the power of 250W, drying the obtained product in a drying oven at 5h and the drying temperature of 100 ℃, and mechanically granulating and sieving the dried solid through a production line to obtain the antibacterial composite material for the air conditioner.
Example 4
Preparing a polydopamine antibacterial agent:
s1, mixing a dopamine hydrochloride solution with the mass concentration of 0.05 g/ml and a sodium carbonate solution with the mass concentration of 30% in a volume ratio of 1:1, heating in a water bath at 55 ℃ to react for 12: 12 h, centrifuging the obtained reaction solution, washing with methanol, and drying in a constant temperature oven at 100 ℃ for 2: 2 h to obtain polydopamine solid;
s2, drying nano zinc oxide with the particle size of 50 nm in a baking oven for 20 h at the temperature of 100 ℃, fully mixing the dried nano zinc oxide with absolute ethyl alcohol, performing ultrasonic treatment on the tip for 20 min, adding KH560 with the mass concentration of 5% and the mass percentage of 10% of the nano zinc oxide for surface treatment, stirring for reaction for 4h under the water bath heating condition of 80 ℃, filtering, washing filter residues with absolute ethyl alcohol for 2 times, drying for 18 h at the temperature of 100 ℃ in the baking oven, grinding with a ball mill, sieving for 100 meshes for standby, and obtaining modified nano zinc oxide;
s3, fully crushing hinokitiol solid, sieving with a 200-mesh sieve to obtain hinokitiol powder, adding 5 wt% of benzalkonium bromide and 50 wt% of absolute ethyl alcohol into 45 wt% of hinokitiol, and carrying out ultrasonic treatment to uniformly disperse the hinokitiol powder to obtain modified hinokitiol;
s4, adding 40. wt% of polydopamine solid, 2. wt% of modified nano zinc oxide, 3. wt% of sodium dodecyl benzene sulfonate and 40. wt% of absolute ethyl alcohol into 15. wt% of modified hinokitiol, carrying out ultrasonic treatment on the mixed solution until the mixed solution is completely and uniformly mixed, carrying out microwave treatment for 15 min with the power of 100. W, filtering, and drying 2. h in a 100 ℃ incubator to obtain the polydopamine antibacterial agent.
Preparing silane modified nano titanium dioxide particles:
drying nano titanium dioxide in a drying oven at 100 ℃, adding 3 wt% of perfluorodecyl trimethoxy silane and 37 wt% of dried nano titanium dioxide into 60 wt% of absolute ethyl alcohol, fully and uniformly stirring, and then carrying out centrifugal filtration, washing and drying for 2 h to obtain nano titanium dioxide particles modified by silane.
Preparing an antibacterial composite material for an air conditioner:
30. 30 wt percent of TPE elastomer, 15. 15 wt percent of magnesium silicate with the particle size of 3000 meshes, 5.5 wt percent of tourmaline powder mixture, 0.5. 0.5 wt percent of diamond powder with the particle size of 1000 meshes, 5.5 wt percent of activated carbon and 6. 6 wt percent of nano titanium dioxide particles modified by silane are ground by a ball mill to 1.5 h with the rotating speed of 1000 r/min, wherein the mass ratio of the tourmaline powder mixture is 8:2 tourmaline powder and phospholanthanum cerium powder;
fully dispersing fully mixed solid powder in 33 wt% deionized water after ultrasonic treatment for 0.5h, adding 1 wt% polydopamine antibacterial agent and 4 wt% castor oil, fully and uniformly stirring in a stirrer, reacting for 10 min by using microwaves with the power of 250W, drying the obtained product in an oven for 3 h, drying at the temperature of 95 ℃, mechanically granulating and sieving the dried solid through a production line to obtain the antibacterial composite material for the air conditioner.
Example 5
Preparing a polydopamine antibacterial agent:
s1, mixing a dopamine hydrochloride solution with the mass concentration of 0.05 g/ml and a sodium carbonate solution with the mass concentration of 30% in a volume ratio of 1:1, heating in a water bath at 55 ℃ to react for 12: 12 h, centrifuging the obtained reaction solution, washing with methanol, and drying in a constant temperature oven at 100 ℃ for 2: 2 h to obtain polydopamine solid;
s2, drying nano zinc oxide with the particle size of 50 nm in a baking oven for 20 h at the temperature of 100 ℃, fully mixing the dried nano zinc oxide with absolute ethyl alcohol, performing ultrasonic treatment on the tip for 20 min, adding KH560 with the mass concentration of 5% and the mass percentage of 10% of the nano zinc oxide for surface treatment, stirring for reaction for 4h under the water bath heating condition of 80 ℃, filtering, washing filter residues with absolute ethyl alcohol for 2 times, drying for 18 h at the temperature of 100 ℃ in the baking oven, grinding with a ball mill, sieving for 100 meshes for standby, and obtaining modified nano zinc oxide;
s3, fully crushing hinokitiol solid, sieving with a 200-mesh sieve to obtain hinokitiol powder, adding 1 wt% of benzalkonium bromide and 50 wt% of absolute ethyl alcohol into 49 wt% of hinokitiol, and carrying out ultrasonic treatment to uniformly disperse the hinokitiol powder to obtain modified hinokitiol;
s4, adding 40. wt% of polydopamine solid, 8. wt% of modified nano zinc oxide, 3. wt% of sodium dodecyl sulfate and 37. wt% of absolute ethyl alcohol into 12. wt% of modified hinokitiol, carrying out ultrasonic treatment on the mixed solution until the mixed solution is completely and uniformly mixed, carrying out microwave treatment for 15 min with the power of 100. W, filtering, and drying 2. h in a 100 ℃ incubator to obtain the polydopamine antibacterial agent.
Preparing silane modified nano titanium dioxide particles:
drying nano titanium dioxide in a drying oven at 100 ℃, adding 1 percent wt percent of perfluoro decyl trimethoxy silane and 39 percent wt percent of dried nano titanium dioxide into 60 percent wt percent absolute ethyl alcohol, fully and uniformly stirring, and then carrying out centrifugal filtration, washing and drying for 2 h to obtain nano titanium dioxide particles modified by silane.
Preparing an antibacterial composite material for an air conditioner:
30. 30 wt percent of TPE elastomer, 15. 15 wt percent of magnesium silicate with the particle size of 3000 meshes, 5.5 wt percent of tourmaline powder mixture, 0.5. 0.5 wt percent of diamond powder with the particle size of 1000 meshes, 5.5 wt percent of activated carbon and 6. 6 wt percent of nano titanium dioxide particles modified by silane are ground by a ball mill to 1.5 h with the rotating speed of 1000 r/min, wherein the mass ratio of the tourmaline powder mixture is 8:2 tourmaline powder and phospholanthanum cerium powder;
fully dispersing fully mixed solid powder in 31 wt% deionized water after ultrasonic treatment for 0.5h, adding 3 wt% polydopamine antibacterial agent and 4 wt% castor oil, fully and uniformly stirring in a stirrer, reacting for 10 min by using microwaves with the power of 300W, drying the obtained product in an oven for 3 h, drying at the temperature of 95 ℃, mechanically granulating and sieving the dried solid through a production line to obtain the antibacterial composite material for the air conditioner.
Comparative example 1
Comparative example 1 differs from example 1 in that the polydopamine antibacterial agent was not added and the rest of the procedure was identical.
30. 30 wt percent of TPE elastomer, 19. 19 wt percent of magnesium silicate with the particle size of 3000 meshes, 5.5 wt percent of tourmaline powder mixture, 0.5. 0.5 wt percent of diamond powder with the particle size of 1000 meshes, 5.5 wt percent of activated carbon and 6. 6 wt percent of nano titanium dioxide particles modified by silane are ground by a ball mill to 1.5 h with the rotating speed of 1000 r/min, wherein the mass ratio of the tourmaline powder mixture is 8:2 tourmaline powder and phospholanthanum cerium powder;
and (3) fully dispersing fully mixed solid powder in 30-wt% deionized water by ultrasonic treatment of 0.5-h, adding 4-wt% castor oil, fully and uniformly stirring in a stirrer, reacting for 10 min by using microwaves with the power of 200-W, drying the obtained product in an oven for 3-h, drying at the temperature of 95 ℃, and mechanically granulating and sieving the dried solid by a production line to obtain the antibacterial composite material for the air conditioner.
Comparative example 2
Comparative example 2 differs from example 1 in that the nano titanium dioxide particles treated without adding silane, in mass percent, the antibacterial composite material for air conditioner comprises the following components: 32 The process is consistent with the rest, comprising weight percent of TPE elastomer, 18 wt percent of magnesium silicate with the particle size of 3000 meshes, 5 wt percent of tourmaline powder mixture, 0.5 wt percent of diamond powder with the particle size of 1000 meshes, 6.5 wt percent of activated carbon, 30 wt percent of deionized water, 4 wt percent of polydopamine antibacterial agent and 4 wt percent of castor oil.
Antibacterial ratio (%) = [ (Ct-Tt)/Ct ] ×100%, where Ct: viable count, tt, obtained 24h after inoculation of the blank: the viable count obtained by 24h was set after inoculation of the example (or comparative).
The material particles obtained in examples 1-5 and comparative examples 1-2 were made into modules by injection molding, antibacterial property tests were conducted according to GB/T31402-2015, the blank samples were all made into polypropylene blocks by using existing polypropylene particles, and antibacterial tests were conducted on E.coli, and the results are shown in the following table:
the same procedure was used to test for the antimicrobial activity of staphylococcus aureus and the results are shown in the following table:
the material particles obtained in the examples 1-2 and the comparative examples 1-2 are made into modules by injection molding, and are placed in an air outlet duct of a central air conditioner, and antibacterial performance tests are carried out according to GB/T21551.3-2010, wherein blank group samples are made into polypropylene blocks by adopting the existing polypropylene particles, and the test is carried out by using escherichia coli for test: 2 h, the test results are as follows:
as shown by the test results, the antibacterial composite material prepared by the invention has more excellent antibacterial performance and high antibacterial rate compared with common polypropylene plastic no matter the antibacterial composite material is directly inoculated with bacteria or used in running air conditioners; the results of comparative examples 1 and 2 show that the nano titanium dioxide is combined with the polydopamine antibacterial agent, so that the antibacterial effect of the prepared material is better.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (9)
1. An antibacterial composite material for an air conditioner comprises the following components in percentage by mass:
28-40% of TPE elastomer, 15-25% wt% of magnesium silicate, 2-5% of tourmaline powder mixture, 0.4-0.6 wt% of diamond powder, 5-8 wt% of activated carbon, 5-8 wt% of nano titanium dioxide particles modified by silane, 1-4% of polydopamine antibacterial agent, 1-5 wt% of surfactant and 30-40% wt% of deionized water;
the preparation of the polydopamine antibacterial agent is as follows:
s1, mixing a dopamine hydrochloride solution with the mass concentration of 0.05 g/ml and a sodium carbonate solution with the mass concentration of 30% in a volume ratio of 1:1, heating in a water bath at 55 ℃ for reaction for 10-12 h, centrifuging the obtained reaction solution, washing with methanol, and drying in a constant temperature oven at 100 ℃ for 2 h to obtain polydopamine solid;
s2, drying nano zinc oxide with the particle size of 50-100 nm in an oven for 18-24 hours at the temperature of 80-100 ℃, fully mixing the dried nano zinc oxide with absolute ethyl alcohol, performing ultrasonic treatment on the tip for 20-30 minutes, adding silane coupling agent KH560 with the mass concentration of 5% and the mass concentration of 10% of the nano zinc oxide for surface treatment, stirring and reacting for 4-5 h under the water bath heating condition of 80 ℃, filtering, washing filter residues with absolute ethyl alcohol for 2-3 times, drying in the oven at the temperature of 100 ℃ for 12-24 h, grinding with a ball mill, and sieving for 100-400 meshes for standby at the rotating speed of 700-1000 r/min to obtain modified nano zinc oxide;
s3, fully crushing hinokitiol solid, sieving with a 200-mesh sieve to obtain hinokitiol powder, adding benzalkonium bromide and absolute ethyl alcohol, and carrying out ultrasonic treatment on the mixture to obtain 0.5h so as to uniformly disperse the hinokitiol powder and obtain modified hinokitiol;
s4, adding polydopamine solid, modified nano zinc oxide, a surfactant and absolute ethyl alcohol into the modified hinokitiol, carrying out ultrasonic treatment on the mixed solution for 0.5-h until the mixed solution is completely and uniformly mixed, then carrying out microwave treatment for 15-25 min, filtering, and drying in a constant temperature oven at 100 ℃ for 2-h to obtain the polydopamine antibacterial agent, wherein the microwave treatment power is 100-200W.
2. The antibacterial composite material for air conditioners according to claim 1, wherein: the grain size of the tourmaline powder mixture is 1500-2000 meshes, the grain size of the diamond powder is 1000-1500 meshes, and the magnesium silicate is ground by a grinder and has a grain size of 3000-4000 meshes.
3. The antibacterial composite material for air conditioners according to claim 1, wherein: the surfactant in the antibacterial composite material component for the air conditioner is one or more of castor oil, polyethylene glycol and carboxymethyl cellulose.
4. The antibacterial composite material for air conditioners according to claim 1, wherein: the tourmaline powder mixture is a mixture of tourmaline powder and phospholanthanum cerium powder, and the mass ratio of the tourmaline powder to the phospholanthanum cerium powder is 8:2.
5. The antibacterial composite material for air conditioners according to claim 1, wherein: in the step S3, the components of hinokitiol, benzalkonium bromide and absolute ethyl alcohol are 30-50 wt percent: 1-5 wt%: 30-50 wt%.
6. The antibacterial composite material for air conditioners according to claim 1, wherein: in the step S4, the components of the modified hinokitiol, polydopamine solid, modified nano zinc oxide, surfactant and absolute ethyl alcohol are 10-15 wt percent: 30-50 wt%: 2-10 wt%: 1-4 wt%: 20-50% wt%.
7. The antibacterial composite material for air conditioners according to claim 1, wherein: in step S4, the surfactant is one of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
8. The antibacterial composite material for air conditioners according to claim 1, wherein: the specific preparation process of the nano titanium dioxide particles modified by silane is as follows:
drying nano titanium dioxide in an oven at 100-120 ℃, adding perfluorodecyl trimethoxy silane into absolute ethyl alcohol, fully stirring and carrying out ultrasonic treatment to obtain silane solution; adding the high-temperature dried nano titanium dioxide into a silane solution, fully and uniformly stirring, and then carrying out centrifugal filtration, washing and drying 2 h to obtain nano titanium dioxide particles modified by silane; wherein the composition ratio of the dried nano titanium dioxide, the perfluorodecyl trimethoxy silane and the absolute ethyl alcohol is 36-45 wt percent: 1-4 wt%: 40-65 wt percent.
9. The method for preparing an antibacterial composite material for an air conditioner according to any one of claims 1 to 8, characterized in that: the specific preparation process of the antibacterial composite material for the air conditioner comprises the following steps:
grinding TPE elastomer, magnesium silicate, tourmaline powder mixture, diamond powder, activated carbon and nano titanium dioxide particles modified by silane by a ball mill according to mass percent, wherein the rotating speed is 900-1100 r/min, and the time is 1-2 h, so that the components are fully mixed;
fully dispersing fully mixed solid powder in deionized water by ultrasonic treatment of 0.5-1 h, adding a polydopamine antibacterial agent and a surfactant, fully stirring uniformly in a stirrer, reacting for 5-15 min by a microwave method, wherein the microwave treatment power is 200-300W, drying the obtained product in an oven at the drying temperature of 95-100 ℃, mechanically granulating and sieving the dried solid by a production line to obtain the antibacterial composite material for the air conditioner.
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