CN103333571B - For the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process - Google Patents
For the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process Download PDFInfo
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- CN103333571B CN103333571B CN201310253662.5A CN201310253662A CN103333571B CN 103333571 B CN103333571 B CN 103333571B CN 201310253662 A CN201310253662 A CN 201310253662A CN 103333571 B CN103333571 B CN 103333571B
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- Prior art keywords
- water
- nano
- heat exchanger
- hydrophilic coating
- exchanger fin
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- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000004378 air conditioning Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 3
- 239000001433 sodium tartrate Substances 0.000 description 3
- 229960002167 sodium tartrate Drugs 0.000 description 3
- 235000011004 sodium tartrates Nutrition 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- OVMJVEMNBCGDGM-UHFFFAOYSA-N iron silver Chemical compound [Fe].[Ag] OVMJVEMNBCGDGM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000012543 microbiological analysis Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.This coating comprises following composition: with the macromolecular compound 3 ~ 30% of hydrophilic radical, the inorganic nano material 0.05 ~ 1% with anti-microbial effect, solidifying agent 0.3 ~ 5%, flow agent 0.02 ~ 0.2%, solubility promoter 2 ~ 10%.Wherein, the inorganic nano material with anti-microbial effect consists of the following composition: nano-oxide 2 ~ 10%, silver salt or Nano silver solution 0.1 ~ 2%, reductive agent 0.1 ~ 2%, stablizer 0.1 ~ 1%, water surplus.The inorganic nano material in the present invention with anti-microbial effect has good stability in system, and antibacterial and mouldproof performance and wetting ability are unattenuated after complete processing, in use can maintain lastingly; And addition is little, cost performance is high, does not affect the processing characteristics in later stage.
Description
Technical field
The present invention relates to a kind of water-borne coatings, particularly a kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
Background technology
In recent years, along with the continuous promotion of national policy and energy-saving and environmental protection, low-carbon (LC) idea constantly universal, the energy-efficient Developing mainstream becoming air conditioner industry.And as the important component part of conditioner, the high performance of heat exchanger also becomes trend of the times.
The fin surface of heat exchanger is general all through hydrophilicity-imparting treatment, after treatment, fin surface has wetting ability, and the dissolved water when water of condensation that it is adhered to and defrosting can flow away rapidly along its surface, thus avoid formation " water bridge " between fin to block air channel, improve heat exchanger effectiveness.The hydrophilicity-imparting treatment of fin surface is all generally form hydrophilic coating by coating hydrophilic coating to realize, and namely forms hydrophilic coating by the aluminium foil machine-shaping of surface-coated hydrophilic coating or shaping rear coating hydrophilic coating.
Because heat exchanger runs under wet cooling condition of being everlasting, moistening and dark environment provides good growing environment to microorganism.So after conditioner use certain hour, the positions such as the fin of heat exchanger are easy to breed bacteria and mould, have a strong impact on the Air quality in environment for use, particularly relatively narrow and small in internal space field of employment, such as automative air conditionings etc., make people produce sense of discomfort, work the mischief to health.
Meanwhile, growing of microorganism also can damage the coating on fin, can badly influence the wetting ability of coating, thus have influence on the heat exchange efficiency of heat exchanger, cause air-conditioning Energy Efficiency Ratio cannot long sustaining, also can reduce the work-ing life of air-conditioning simultaneously, cause the loss of resource and the energy.
Therefore, if fin has the hydrophilic function also having antibacterial and mouldproof simultaneously, not only contribute to the Air quality maintaining operation of air conditioner indoor, build healthy living environment, and can prevent bacterium and mould from corroding fin and coating, wetting ability is more lasting, and the Energy Efficiency Ratio of air-conditioning is able to long sustaining, more energy-conservation.
Application for a patent for invention CN1721479A proposes a kind of hydrophilic antimicrobial composition for vehicle air-conditioner evaporator, contains hydrophilic organic polymers, smoothing agent, antiseptic-germicide and deionized water, and its antiseptic-germicide is acetaldehyde and Ti (OH)
x(PO)
y-znO, content respectively can up to 2wt% and 10wt%, and its principle is that antiseptic-germicide contact with oxygen or water and produces hydrogen peroxide, thus passes through oxidizing reaction decomposing organic matter, elimination fungus and bacterium.Application for a patent for invention CN1776345A proposes a kind of anti-biotic material for heat-exchanger surface, and this material is the nanoparticle of the carrier using titanium oxide as zinc, and its addition is 2 ~ 40% of hydrophilic layer, realizes its antibacterial by photocatalysis.Utility model patent CN201191103Y provides a kind of super hydrophilic antimicrobial type aluminium foil for heat exchanger, wherein relates to and adds nano-oxide and silver iron compound to realize the technical scheme of hydrophilic aluminium foil germ resistance at hydrophilic functional layer.Application for a patent for invention CN101892000A relates to a kind of antibacterial mildew-proof hydrophilic coating, its anti-biotic material adopts the nano photo-catalytic colloid of copper clad, by slowly dripping obtained antibacterial mildew-proof hydrophilic coating in hydrophilic resin under the speed agitation condition of 3000 ~ 5000 revs/min.
When adopting the photocatalyst material of titanium dioxide and so on titaniferous as anti-biotic material, its germ resistance must be realized by photocatalysis, namely must when there being abundant illumination its anti-microbial effect of competence exertion, and under heat exchanger is all in dark Working environment usually, therefore use the anti-biotic material of photocatalyst type to be difficult to play good anti-microbial effect in such circumstances.Meanwhile, because photocatalyst is to organic Decomposition, coating itself also can be destroyed, and causes the decline of coating performance.And above-mentioned patent application is also mentioned, the addition of such anti-biotic material is higher, and this improves manufacturing cost on the one hand, also result in the difficulty of post-production on the other hand.The interpolation of some material is more difficult, needs just can join in coating in high speed dispersion situation, and this causes restriction to actual production, is also difficult to ensure good stability simultaneously.
Silver class anti-biotic material germ-killing efficiency is high, and is less than the photocatalyst material of titanium dioxide class by the impact of light, so be more suitable for the darker Working environment of heat exchanger.Above-mentioned patent application also mentions that silver iron compound is to realize germ resistance.But because silver ions is easy to stripping, cause loss, be difficult to the persistence realizing germ resistance, the germ resistance namely in post-production technique and use procedure is difficult to maintain.On the other hand, silver ions is easily reduced, and its existence easily causes variable color, even occurs precipitation.
Current hydrophilic coating product on the market seldom possesses antibacterial and mouldproof performance, and some only possess the germ resistance at initial stage, is difficult to maintain in post-production and actual use procedure.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, provides a kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
Another object of the present invention is to provide the preparation method of the described waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
Another object of the present invention is to provide the application of the described waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
Object of the present invention is achieved through the following technical solutions: a kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, comprises following composition by mass percentage: with the macromolecular compound 3 ~ 30% of hydrophilic radical, the inorganic nano material 0.05 ~ 1% with anti-microbial effect, solidifying agent 0.3 ~ 5%, flow agent 0.02 ~ 0.2%, solubility promoter 2 ~ 10%;
The described waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, also comprises water, and water is surplus;
The described macromolecular compound with hydrophilic radical is one in the homopolymer of water-soluble monomer, the multipolymer of water-soluble monomer, polyoxyethylene glycol, polypropylene glycol, polymine, polyvinyl alcohol, polyvinyl butyral acetal, carboxymethyl cellulose, Natvosol, polyoxyethylene, Lalgine, sodium alginate, starch and chitosan or at least two kinds;
Described water-soluble monomer is with carboxylic acid group, sulfonic group, hydroxyl, amido, the monomer of the hydrophilic radicals such as amide group, is preferably vinylformic acid, methacrylic acid, sodium acrylate, sodium methacrylate, zinc acrylate resin, zinc methacrylate, methylene-succinic acid, cis-butenedioic anhydride, methacrylic acid phosphoric acid ester, sodium p styrene sulfonate, allyl sulphonic acid, sodium allyl sulfonate, sodium vinyl sulfonate, vinylformic acid sodium sulfonate, methacrylic sulfonic acids sodium, 3-allyloxy-2 hydroxyl-1-propane sulfonic acid sodium, vinyl hydroxyethyl ether, hydroxy butyl vinyl ether, acrylamide, Methacrylamide, n-methylolacrylamide, hydroxyethyl acrylamide, dimethylaminoethyl methacrylate, diacetone-acryloamide(DAA), NVP, dimethyl diallyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride, methylacryoyloxyethyl-n-hexadecyl-alkyl dimethyl ammonium chloride, methylacryoyloxyethyl-o-chlorobenzyl-alkyl dimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl tributyl ammonium chloride, to vinyl benzyl tributyl phosphonium chloride, 4-vinylpridine, one in N-acetamido-4-vinylpridine and methacryloxypropyl dodecyl bromopyridine or at least two kinds, be more preferably dimethylaminoethyl methacrylate, dimethyl diallyl ammonium chloride, at least one in vinyl benzyl tributyl phosphonium chloride, 4-vinylpridine, vinylformic acid, methacrylic acid, acrylamide, Methacrylamide, NVP and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride,
The homopolymer of described water-soluble monomer or the multipolymer of water-soluble monomer prepare as follows:
1. with water, the water-soluble thermal initiator of 0.5 ~ 2 mass parts is mixed with water-soluble thermal initiator solution;
2. with water, the water-soluble monomer of 5 ~ 30 mass parts is dissolved post-heating to 70 ~ 95 DEG C, drip the step 1. middle water-soluble thermal initiator solution prepared, continue reaction 2 ~ 5 hours, whole process leads to nitrogen;
3. be cooled to 25 ~ 30 DEG C, obtain the homopolymer of water-soluble monomer or the multipolymer of water-soluble monomer.
Step 1. described in water-soluble thermal initiator comprise Sodium Persulfate, Potassium Persulphate, ammonium persulphate, 4,4 '-azo two (4-cyanopentanoic acid) and azo-bis-isobutyrate hydrochloride; Be more preferably at least one in Sodium Persulfate, azo-bis-isobutyrate hydrochloride;
Step 1. described in the concentration of water-soluble thermal initiator solution be preferably as mass percent 3 ~ 5%;
The time of the dropping described in step (2) is preferably 30 minutes;
The molecular weight of the described macromolecular compound with hydrophilic radical is 5000 ~ 1000000, is preferably 8000 ~ 200000;
The described inorganic nano material with anti-microbial effect is nano-oxide carrying silver antimicrobials, is grouped into by following one-tenth by mass percentage: nano-oxide 2 ~ 10%, silver salt or Nano silver solution 0.1 ~ 2%, reductive agent 0.1 ~ 2%, stablizer 0.1 ~ 1%, water surplus;
The content of described reductive agent is preferably mass percent 0.1 ~ 0.5%;
Described nano-oxide is preferably the nano-oxide that particle diameter is 10 ~ 80nm, is more preferably the one in nano silicon, nano aluminium oxide, nano zircite, nano-sized iron oxide, nano zine oxide and nano titanium oxide or at least two kinds;
Described nano-oxide is dissolved colloidal state or powdered form;
Described silver salt is Ag
3pO
4, AgNO
3, Ag
2s
2o
3, CH
3cOOAg, AgClO
4with the one in AgF or at least two kinds;
Described Nano silver solution is commercially available Nano silver solution, comprises the one in AGS-WMB1000A, AGS-WMB1000B and AGS-WMB1000B of the JDTKS-001 of the large nanosecond science and technology in Shanxi, JDTKS-005, the positive nanosecond science and technology in Shanghai or at least two kinds;
Described reductive agent is one in sodium hypophosphite, hydrazine hydrate, formaldehyde, xitix, glucose, tartrate, V-Brite B, tannin, quinhydrones, Trisodium Citrate and sodium borohydride or at least two kinds;
Described stablizer is one in ethanol, Virahol, propyl carbinol, the trimethyl carbinol, hexalin, ethylene glycol, glycerol, sorbyl alcohol, polysorbate, polyoxyethylene glycol, polyvinyl alcohol, Polyvinylpyrolidone (PVP), gelatin, dodecyl mercaptans, trolamine, silane coupling agent, titanate coupling agent and zirconium ester coupling agent or at least two kinds;
The described inorganic nano material with anti-microbial effect is prepared by the method comprising following steps:
(1) nano-oxide is mixed with nano-oxide aqueous dispersions;
(2) silver salt is mixed with silver salt solution, or with water, Nano silver solution dilution is obtained nanometer silver diluent;
(3) reductive agent is mixed with the reductive agent aqueous solution;
(4) the nano-oxide aqueous dispersions that step (1) is prepared is added under agitation in the silver salt solution or nanometer silver diluent that step (2) prepares, add water and the stablizer of surplus, pH is kept 8 ~ 10 to react, then add the reductive agent aqueous solution that step (3) is prepared, then continue reaction; Then filter, dry, obtain the inorganic nano material with anti-microbial effect;
Wherein, the content of each composition is as follows by mass percentage: nano-oxide 2 ~ 10%, silver salt or Nano silver solution 0.1 ~ 2%, reductive agent 0.1 ~ 2%, stablizer 0.1 ~ 1%, water surplus;
The content of described reductive agent is preferably mass percent 0.1 ~ 0.5%;
The concentration of the nano-oxide aqueous dispersions described in step (1) is preferably mass percent 10 ~ 50%;
The concentration of the silver salt solution described in step (2) is preferably 0.1 ~ 0.5mol/L;
The concentration of the nanometer silver diluent described in step (2) is preferably 0.1 ~ 0.5mol/L;
The concentration of the reductive agent aqueous solution described in step (3) is preferably 0.1 ~ 0.5mol/L;
The rotating speed of the stirring described in step (4) is preferably 50 ~ 500rpm;
Maintenance pH described in step (4) was preferably 5 ~ 30min 8 ~ 10 times of carrying out reacting;
The time of the continuation reaction suddenly described in (4) is preferably 10 ~ 30min;
The condition optimization of the drying described in step (4) is dry 5 ~ 48h in 50 ~ 200 DEG C; Be more preferably dry 8 ~ 24h in 80 ~ 150 DEG C; Most preferably be dry 10 ~ 24h in 80 ~ 150 DEG C;
The described particle diameter with the inorganic nano material of anti-microbial effect is 10 ~ 200nm, is more preferably 10 ~ 80nm, most preferably is 30 ~ 80nm; It is easy to be dispersed in above-mentioned with in the macromolecular compound of hydrophilic radical;
Described solidifying agent is one or both in nitrogen containing derivative and polyhydroxy-alcohol;
Described nitrogen containing derivative is the material with beta-hydroxy alkylamide structural formula, as the EP-HA320 of DYNAPOL company;
Described polyhydroxy-alcohol to comprise in molecular structure containing the water-soluble polyol of at least three hydroxyls, specifically comprise glycerine, the polymerization degree be 3 ~ 10 polyglycerol, TriMethylolPropane(TMP), the dimer of TriMethylolPropane(TMP), tetramethylolmethane and tetramethylolmethane dimer at least one;
Described flow agent is nonionogenic tenside, anion surfactant, anionic and nonionic tensio-active agent known by the art, comprise alkylphenol polyoxyethylene, alkylphenol polyoxyethylene sulfonate, alkylphenol polyoxyethylene vitriol, alkyl diphenyl ether disulfonate, alkyl diphenyl ether dithionate, alkylbenzene sulfonate, alkyl sulfate, alkylsulfonate, alkyl-sulphate, aliphatic alcohol polyoxyethylene sulfonate, fatty alcohol polyoxyethylene ether sulfate, preferred alkyl diphenyl ether sulfonate and/or fatty alcohol polyoxyethylene ether sulfate;
Described solubility promoter is alcohol and/or ether, is preferably the one in methyl alcohol, ethanol, Virahol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, diethylene glycol ether and butyl or at least two kinds;
The preparation method of the described waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, comprise following steps: by with the mixing of the macromolecular compound of hydrophilic radical, the inorganic nano material with anti-microbial effect, solidifying agent, flow agent, solubility promoter and water, after stirring, obtain the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process; Wherein, each composition by mass percentage, as follows: with the macromolecular compound 3 ~ 30% of hydrophilic radical, the inorganic nano material 0.05 ~ 1% with anti-microbial effect, solidifying agent 0.3 ~ 5%, flow agent 0.02 ~ 0.2%, solubility promoter 2 ~ 10%, water surplus;
The described waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process is specially adapted to heat exchanger of air condition, following steps are comprised: by the organic crylic acid primary coat known by the waterborne antibacterial mildew-proof hydrophilic coating supporting industry personnel being used for heat exchanger fin surfaces process that obtain, organic epoxy primary coat or inorganic passivation primary coat, be coated on aluminium foil surface and obtain coating during application.
The present invention has following advantage and effect relative to prior art:
(1) the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process provided by the invention, the nano-oxide carrying silver antimicrobials used has good stability in system, antibacterial and mouldproof performance and wetting ability are unattenuated after complete processing, in use can maintain lastingly.
(2) provided by the invention little for nano-oxide carrying silver antimicrobials addition in the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process, cost performance is high, does not affect the processing characteristics in later stage.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
In following examples, mass unit all adopts g.
Embodiment 1
A kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, be grouped into by following one-tenth by mass percentage: polyacrylic acid (molecular weight 200000) 5g, silver-carrying nano silicon-dioxide 0.1g, tetramethylolmethane 5g, alkylphenol polyoxyethylene 0.02g, ethanol 5g, water complements to 100g.
(1) polyacrylic acid prepares as follows:
1. 1g Sodium Persulfate is mixed with the sodium persulfate aqueous solution that concentration is mass percent 3%;
2. add in reactor by 5g vinylformic acid and 61.7 water, stir post-heating to 80 DEG C, and drip the step 1. middle sodium persulfate aqueous solution prepared, time for adding is 30 minutes, and react 4 hours, whole process leads to nitrogen;
3. be cooled to 25 DEG C, obtain polyacrylic acid (it is 200000 that gel permeation chromatography records molecular weight).
(2) silver-carrying nano silicon-dioxide prepares as follows:
1. 5g nano silicon (median size is 10nm, powdered form) is mixed with the nano silicon aqueous dispersions that mass percentage concentration is 15%;
2. by 0.1gAg
3pO
4be mixed with the Ag that volumetric molar concentration is 0.1mol/L
3pO
4the aqueous solution;
3. 0.2g glucose is mixed with the D/W that volumetric molar concentration is 0.2mol/L;
4. nano silicon aqueous dispersions step 1. prepared adds the Ag that 2. step is prepared under the agitation condition of 200rpm
3pO
4in the aqueous solution, add the water (total amount of water used in preparation process is 93.7g) of surplus, add 1g ethanol, pH is kept to be 8 with ammoniacal liquor, the D/W that 3. step is prepared is added after 15min, filter after 10min, dry 24h in 80 DEG C, the silver-carrying nano silicon-dioxide that median size is 32nm can be obtained.
(3) for the preparation of the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process: by above-mentioned formula, polyacrylic acid, silver-carrying nano silicon-dioxide, tetramethylolmethane, alkylphenol polyoxyethylene, second alcohol and water are mixed, obtains the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
(4) detect:
On the model of precoating organic crylic acid primary coat, manual scraper plate obtains antibacterial mildew-proof hydrophilic coating (baking condition is 260 DEG C × 25s), then volatile oil immersion, flowing water dipping is carried out according to the method for the technique wetting ability specified in TS/T95.2-2009 and protracted hydrophilicity, and Erichsen test.Untreated, volatile oil soaks and model after flowing water dipping all carries out antibacterium and resistance to mould test (entrusting microbiological analysis inspection center of Guangdong Province to carry out correlation detection): antibacterium performance measures according to the method for HG/T3950-2007 appendix A; Fungus resistance can measure according to the method for GB/T1741-2007.The results are shown in Table 1.
Embodiment 2
A kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, be grouped into by following one-tenth by mass percentage: polyacrylic acid (molecular weight 100000) 8g, silver-carrying nano aluminum oxide 0.5g, glycerine 2g, alkyl phenol polyethenoxy ether sodium sulfate 0.02g, Virahol 2g, water complements to 100g.
(1) polyacrylic acid prepares as follows:
1. 0.5g azo-bis-isobutyrate hydrochloride is mixed with the aqueous solution that mass percentage concentration is 5%;
2. add in reactor by 10g vinylformic acid and 80g water, stir post-heating to 70 DEG C, and drip the step 1. middle aqueous solution prepared, time for adding is 30 minutes, and react 5 hours, whole process leads to nitrogen;
3. be cooled to 25 DEG C, obtain polyacrylic acid (it is 100000 that gel permeation chromatography records molecular weight).
(2) silver-carrying nano aluminum oxide prepares as follows:
1. 2g nano aluminium oxide (median size 20nm, dissolved colloidal state) is mixed with the nano aluminium oxide aqueous dispersions that mass percentage concentration is 10%;
2. 0.2gAgF is mixed with the AgF aqueous solution that volumetric molar concentration is 0.1mol/L;
3. 0.1g sodium tartrate is mixed with the sodium tartrate aqueous solution that volumetric molar concentration is 0.1mol/L;
4. nano aluminium oxide aqueous dispersions step 1. prepared adds in the AgF aqueous solution that 2. step prepare under the agitation condition of 100rpm, add the water (total amount of water used in preparation process is 96.7g) of surplus, add 1g ethylene glycol, pH is kept to be 9 with ammoniacal liquor, the sodium tartrate aqueous solution that 3. step is prepared is added after 20min, filter after 20min, dry 15h in 100 DEG C, the silver-carrying nano aluminum oxide that median size is 55nm can be obtained.
(3) for the preparation of the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process: by above-mentioned formula, polyacrylic acid, silver-carrying nano aluminum oxide, glycerine, alkyl phenol polyethenoxy ether sodium sulfate, isopropyl alcohol and water are mixed, obtains the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
(4) detect:
On the model of pre-coating inorganic passivation primary coat, manual scraper plate obtains antibacterial mildew-proof hydrophilic coating, and sampling and testing method, with embodiment 1, the results are shown in Table 1.
Embodiment 3
A kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, be grouped into by following one-tenth by mass percentage: polyoxyethylene glycol (PEG-8000, DOW Chemical) 15g, silver-carrying nano zirconium white 0.05g, TriMethylolPropane(TMP) 0.3g, alkyl diphenyl ether disulfonate 0.2g, propylene glycol monomethyl ether 10g, water complements to 100g.
(1) silver-carrying nano zirconium white prepares as follows:
1. 5g nano zircite (median size is 25nm, dissolved colloidal state) is mixed with the nano zircite aqueous dispersions that mass percentage concentration is 20%;
2. by 0.5gAgClO
4be mixed with the AgClO that volumetric molar concentration is 0.2mol/L
4the aqueous solution;
3. 0.3g xitix is mixed with the aqueous ascorbic acid that volumetric molar concentration is 0.3mol/L;
4. nano zircite aqueous dispersions step 1. prepared adds the AgClO that 2. step is prepared under the agitation condition of 50rpm
4in the aqueous solution, add the water (total amount of water used in preparation process is 93.7g) of surplus, add 0.5g sorbyl alcohol, pH is kept to be 10 with ammoniacal liquor, the aqueous ascorbic acid that 3. step is prepared is added after 5min, filter after 30min, dry 10h in 120 DEG C, the silver-carrying nano zirconium white that median size is 43nm can be obtained.
(2) for the preparation of the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process: by above-mentioned formula, polyoxyethylene glycol, silver-carrying nano zirconium white, TriMethylolPropane(TMP), alkyl diphenyl ether disulfonate, propylene glycol monomethyl ether and water are mixed, obtains the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
(3) detect:
On the model of pre-coating inorganic passivation primary coat, manual scraper plate obtains antibacterial mildew-proof hydrophilic coating, and sampling and testing method, with embodiment 1, the results are shown in Table 1.
Embodiment 4
A kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, comprise following composition by mass percentage: Natvosol (QP-300H, DOW Chemical) 3g, silver-carrying nano silica 1 g, EP-HA3200.5g, fatty alcohol polyoxyethylene ether sulfate 0.1g, propylene-glycol ethyl ether 8g, water complements to 100g.
(1) silver-carrying nano silicon-dioxide prepares as follows:
1. 10g nano silicon (median size is 30nm, dissolved colloidal state) is mixed with the nano silicon aqueous dispersions that mass percentage concentration is 50%;
2. with water, 1gJDTKS-001 is diluted to the water diluent that volumetric molar concentration is 0.3mol/L;
3. 0.5g tannin is mixed with the tannin aqueous solution that volumetric molar concentration is 0.3mol/L;
4. nano silicon aqueous dispersions step 1. prepared adds in the JDTKS-001 water diluent that 2. step prepare under the agitation condition of 500rpm, add the water (total amount of water used in preparation process is 88.4g) of surplus, add 0.1g polyoxyethylene glycol (PEG2000), pH is kept to be 9 with ammoniacal liquor, the tannin aqueous solution that 3. step is prepared is added after 10min, filter after 15min, dry 10h in 150 DEG C, the silver-carrying nano silicon-dioxide that median size is 45nm can be obtained.
(2) for the preparation of the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process: by above-mentioned formula, Natvosol, silver-carrying nano silicon-dioxide, EP-HA320, fatty alcohol polyoxyethylene ether sulfate, propylene-glycol ethyl ether and water are mixed, obtains the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
(3) detect:
On the model of pre-coating inorganic passivation primary coat, manual scraper plate obtains antibacterial mildew-proof hydrophilic coating, and sampling and testing method, with embodiment 1, the results are shown in Table 1.
Embodiment 5
A kind of waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, comprise following composition by mass percentage: (molecular weight is 10000 for methacrylic acid, Methacrylamide and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride multipolymer, monomer weight ratio is 60/35/5) 30g, Ag-carried nanometer titanium dioxide 0.5g, tetramethylolmethane 2g, alkylphenol polyoxyethylene 0.05g, butyl 3g, water complements to 100g.
(1) methacrylic acid, Methacrylamide and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride multipolymer prepare as follows:
1. 2g Sodium Persulfate and azo-bis-isobutyrate hydrochloride mixture (mass ratio 2:1) are mixed with the aqueous solution that mass percentage concentration is 3%;
2. 18g methacrylic acid, 10.5g Methacrylamide and 1.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 3.3g water are added in reactor, stir post-heating to 95 DEG C, drip the step 1. middle aqueous solution prepared, time for adding is 30 minutes, react 2 hours, whole process leads to nitrogen.
3. be cooled to 30 DEG C, obtain methacrylic acid, Methacrylamide and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride multipolymer (it is 10000 that gel permeation chromatography records molecular weight).
(2) Ag-carried nanometer titanium dioxide prepares as follows:
1. 8g nano titanium oxide (median size is 55nm, dissolved colloidal state) is mixed with the nano titanium dioxide water-dispersion liquid that mass percentage concentration is 30%;
2. 2gAGS-WMB1000A is mixed with the water diluent that volumetric molar concentration is 0.5mol/L;
3. 0.5g sodium borohydride is mixed with the sodium borohydride aqueous solution that volumetric molar concentration is 0.5mol/L;
4. nano titanium dioxide water-dispersion liquid step 1. prepared adds in the AGS-WMB1000A water diluent that 2. step prepare under the agitation condition of 200rpm, add the water (total amount of water used in preparation process is 89g) of surplus, add 0.5g Silane coupling agent KH550, pH is kept to be 8 with ammoniacal liquor, the sodium borohydride aqueous solution that 3. step is prepared is added after 30min, filter after 25min, dry 20h in 80 DEG C, the Ag-carried nanometer titanium dioxide that particle diameter is the original position load of 80nm can be obtained.
(2) for the preparation of the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process: by above-mentioned formula, methacrylic acid, Methacrylamide and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride multipolymer, Ag-carried nanometer titanium dioxide, tetramethylolmethane, alkylphenol polyoxyethylene, butyl and water are mixed, obtains the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process.
(3) detect:
On the model of pre-coating inorganic passivation primary coat, manual scraper plate obtains antibacterial mildew-proof hydrophilic coating, and sampling and testing method, with embodiment 1, the results are shown in Table 1.
Comparative example 1
Roughly the same with embodiment 1, its difference is only that this comparative example directly uses Ag
3pO
4as antiseptic-germicide.
On the model of precoating organic crylic acid primary coat, manual scraper plate obtains coating, and sampling and testing method, with embodiment 1, the results are shown in Table 1.
Comparative example 2
Roughly the same with embodiment 1, its difference is only that the median size of the silicon-dioxide of this comparative example is 500nm.
On the model of precoating organic crylic acid primary coat, manual scraper plate obtains coating, and sampling and testing method, with embodiment 1, the results are shown in Table 1.
Comparative example 3
Roughly the same with embodiment 1, its difference is only that this comparative example directly uses nano titanium oxide as antiseptic-germicide.
On the model of precoating organic crylic acid primary coat, manual scraper plate obtains coating, and sampling and testing method, with embodiment 1, the results are shown in Table 1.
Table 1
From table 1, all there is the problem of paint stability difference in comparative example, and germ resistance, mildew resistance and wetting ability can not long sustainings.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. for a waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process, it is characterized in that comprising following composition by mass percentage: with the macromolecular compound 3 ~ 30% of hydrophilic radical, the inorganic nano material 0.05 ~ 1% with anti-microbial effect, solidifying agent 0.3 ~ 5%, flow agent 0.02 ~ 0.2%, solubility promoter 2 ~ 10%;
The described macromolecular compound with hydrophilic radical is one in the homopolymer of water-soluble monomer, the multipolymer of water-soluble monomer, polyoxyethylene glycol, polypropylene glycol, polymine, polyvinyl alcohol, polyvinyl butyral acetal, carboxymethyl cellulose, Natvosol, polyoxyethylene, Lalgine, sodium alginate, starch and chitosan or at least two kinds;
Described water-soluble monomer is the monomer with at least one group in carboxylic acid group, sulfonic group, hydroxyl, amido and amide group;
The described inorganic nano material with anti-microbial effect is nano-oxide carrying silver antimicrobials, is grouped into by following one-tenth by mass percentage: nano-oxide 2 ~ 10%, silver salt or Nano silver solution 0.1 ~ 2%, reductive agent 0.1 ~ 2%, stablizer 0.1 ~ 1%, water surplus;
The described inorganic nano material with anti-microbial effect is prepared by the method comprising following steps:
(1) nano-oxide is mixed with nano-oxide aqueous dispersions;
(2) silver salt is mixed with silver salt solution, or with water, Nano silver solution dilution is obtained nanometer silver diluent;
(3) reductive agent is mixed with the reductive agent aqueous solution;
(4) the nano-oxide aqueous dispersions that step (1) is prepared is added under agitation in the silver salt solution or nanometer silver diluent that step (2) prepares, add water and the stablizer of surplus, pH is kept 8 ~ 10 to react, then add the reductive agent aqueous solution that step (3) is prepared, then continue reaction; Then filter, dry, obtain the inorganic nano material with anti-microbial effect; Described solidifying agent is one or both in nitrogen containing derivative and polyhydroxy-alcohol;
Described flow agent is nonionogenic tenside, anion surfactant or anionic and nonionic tensio-active agent;
Described solubility promoter is alcohol and/or ether.
2. the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process according to claim 1, is characterized in that:
Described nano-oxide is one in nano silicon, nano aluminium oxide, nano zircite, nano-sized iron oxide, nano zine oxide and nano titanium oxide or at least two kinds;
Described silver salt is Ag
3pO
4, AgNO
3, Ag
2s
2o
3, CH
3cOOAg, AgClO
4with the one in AgF or at least two kinds;
Described Nano silver solution is one in JDTKS-001, JDTKS-005, AGS-WMB1000A and AGS-WMB1000B or at least two kinds;
Described reductive agent is one in sodium hypophosphite, hydrazine hydrate, formaldehyde, xitix, glucose, tartrate, V-Brite B, tannin, quinhydrones, Trisodium Citrate and sodium borohydride or at least two kinds;
Described stablizer is one in ethanol, Virahol, propyl carbinol, the trimethyl carbinol, hexalin, ethylene glycol, glycerol, sorbyl alcohol, polysorbate, polyoxyethylene glycol, polyvinyl alcohol, Polyvinylpyrolidone (PVP), gelatin, dodecyl mercaptans, trolamine, silane coupling agent, titanate coupling agent and zirconium ester coupling agent or at least two kinds;
The concentration of the nano-oxide aqueous dispersions described in step (1) is mass percent 10 ~ 50%;
The concentration of the silver salt solution described in step (2) is 0.1 ~ 0.5mol/L;
The concentration of the nanometer silver diluent described in step (2) is 0.1 ~ 0.5mol/L;
The concentration of the reductive agent aqueous solution described in step (3) is 0.1 ~ 0.5mol/L;
The rotating speed of the stirring described in step (4) is 50 ~ 500rpm;
Maintenance pH described in step (4) was 8 ~ 10 times of carrying out reacting is 5 ~ 30min;
The time of the continuation reaction described in step (4) is 10 ~ 30min;
The condition of the drying described in step (4) is dry 5 ~ 48h in 50 ~ 200 DEG C;
The described particle diameter with the inorganic nano material of anti-microbial effect is 10 ~ 200nm.
3. the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process according to claim 1, is characterized in that:
The homopolymer of described water-soluble monomer or the multipolymer of described water-soluble monomer prepare as follows:
1. with water, the water-soluble thermal initiator of 0.5 ~ 2 mass parts is mixed with water-soluble thermal initiator solution;
2. with water, the water-soluble monomer of 5 ~ 30 mass parts is dissolved post-heating to 70 ~ 95 DEG C, drip the step 1. middle water-soluble thermal initiator solution prepared, continue reaction 2 ~ 5 hours, whole process leads to nitrogen;
3. be cooled to 25 ~ 30 DEG C, obtain the homopolymer of water-soluble monomer or the multipolymer of water-soluble monomer.
4. the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process according to claim 3, is characterized in that:
Described water-soluble monomer is vinylformic acid, methacrylic acid, sodium acrylate, sodium methacrylate, zinc acrylate resin, zinc methacrylate, methylene-succinic acid, cis-butenedioic anhydride, methacrylic acid phosphoric acid ester, sodium p styrene sulfonate, allyl sulphonic acid, sodium allyl sulfonate, sodium vinyl sulfonate, vinylformic acid sodium sulfonate, methacrylic sulfonic acids sodium, 3-allyloxy-2 hydroxyl-1-propane sulfonic acid sodium, vinyl hydroxyethyl ether, hydroxy butyl vinyl ether, acrylamide, Methacrylamide, n-methylolacrylamide, hydroxyethyl acrylamide, dimethylaminoethyl methacrylate, diacetone-acryloamide(DAA), NVP, dimethyl diallyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride, methylacryoyloxyethyl-n-hexadecyl-alkyl dimethyl ammonium chloride, methylacryoyloxyethyl-o-chlorobenzyl-alkyl dimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl tributyl ammonium chloride, to vinyl benzyl tributyl phosphonium chloride, 4-vinylpridine, one in N-acetamido-4-vinylpridine and methacryloxypropyl dodecyl bromopyridine or at least two kinds,
Described water-soluble thermal initiator is at least one in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, 4,4'-azos two (4-cyanopentanoic acid) and azo-bis-isobutyrate hydrochloride.
5. the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process according to claim 1, is characterized in that:
The molecular weight of the described macromolecular compound with hydrophilic radical is 5000 ~ 1000000;
Described nitrogen containing derivative is the material with beta-hydroxy alkylamide structural formula;
Described polyhydroxy-alcohol is the water-soluble polyol containing at least three hydroxyls in molecular structure;
Described flow agent is one in alkylphenol polyoxyethylene, alkylphenol polyoxyethylene sulfonate, alkylphenol polyoxyethylene vitriol, alkyl diphenyl ether disulfonate, alkyl diphenyl ether dithionate, alkylbenzene sulfonate, alkyl sulfate, alkylsulfonate, alkyl-sulphate, aliphatic alcohol polyoxyethylene sulfonate and fatty alcohol polyoxyethylene ether sulfate or at least two kinds;
Described solubility promoter is one in methyl alcohol, ethanol, Virahol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, diethylene glycol ether and butyl or at least two kinds.
6. the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process according to claim 5, is characterized in that:
Described nitrogen containing derivative is the EP-HA320 of DYNAPOL company;
At least one in the dimer of the dimer of the polyglycerol that described polyhydroxy-alcohol is glycerine, the polymerization degree is 3 ~ 10, TriMethylolPropane(TMP), TriMethylolPropane(TMP), tetramethylolmethane and tetramethylolmethane.
7. the preparation method of the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process described in any one of claim 1 ~ 6, it is characterized in that comprising following steps: by with the mixing of the macromolecular compound of hydrophilic radical, the inorganic nano material with anti-microbial effect, solidifying agent, flow agent, solubility promoter and water, after stirring, obtain the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process; Wherein, each composition by mass percentage, as follows: with the macromolecular compound 3 ~ 30% of hydrophilic radical, the inorganic nano material 0.05 ~ 1% with anti-microbial effect, solidifying agent 0.3 ~ 5%, flow agent 0.02 ~ 0.2%, solubility promoter 2 ~ 10%, water surplus.
8. the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process described in any one of claim 1 ~ 6 is preparing the application in heat exchanger of air condition.
9. the waterborne antibacterial mildew-proof hydrophilic coating for heat exchanger fin surfaces process according to claim 8 is preparing the application in heat exchanger of air condition, it is characterized in that comprising following steps: described is used for the waterborne antibacterial mildew-proof hydrophilic coating supporting organic crylic acid primary coat of heat exchanger fin surfaces process, organic epoxy primary coat or inorganic passivation primary coat, is coated on aluminium foil surface and obtains coating.
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| CN111334141A (en) * | 2018-12-18 | 2020-06-26 | 山西科启科技有限公司 | Hydrophilic antibacterial coating for automobile air-conditioning evaporator and preparation method thereof |
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