CN118344855B - Low-conductivity corrosion inhibition cooling liquid and preparation method thereof - Google Patents
Low-conductivity corrosion inhibition cooling liquid and preparation method thereof Download PDFInfo
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- 239000000110 cooling liquid Substances 0.000 title claims abstract description 68
- 238000005260 corrosion Methods 0.000 title claims abstract description 35
- 230000007797 corrosion Effects 0.000 title claims abstract description 34
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920001661 Chitosan Polymers 0.000 claims abstract description 71
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 63
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 58
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 27
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 13
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 11
- 229910021538 borax Inorganic materials 0.000 claims abstract description 11
- 239000013530 defoamer Substances 0.000 claims abstract description 11
- XWRLQRLQUKZEEU-UHFFFAOYSA-N ethyl(hydroxy)silicon Chemical compound CC[Si]O XWRLQRLQUKZEEU-UHFFFAOYSA-N 0.000 claims abstract description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 11
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 11
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- -1 silane modified copper powder Chemical class 0.000 claims description 19
- 238000007334 copolymerization reaction Methods 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000002826 coolant Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229920013747 hydroxypolyethylene Polymers 0.000 claims description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000006260 foam Substances 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012809 cooling fluid Substances 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002528 anti-freeze Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a low-conductivity corrosion inhibition cooling liquid and a preparation method thereof, and belongs to the technical field of cooling liquid, wherein the cooling liquid comprises the following raw materials in parts by mass: 55-60 parts of deionized water, 40-45 parts of ethylene glycol, 5-5.5 parts of pentaerythritol, 2-2.5 parts of copolymer of chitosan and polyethylene glycol, 0.5-0.6 part of nano particles, 0.5-0.6 part of sebacic acid, 0.5-0.6 part of borax, 0.4-0.5 part of methylbenzotriazole, 0.3-0.4 part of sodium benzoate, 0.3-0.4 part of sodium silicate, 0.3-0.4 part of 2- (sodium-sulfophenyl) ethyl siloxane, 0.1-0.12 part of sodium hydroxide and 0.01-0.02 part of polyether defoamer; the cooling liquid prepared by the invention has low conductivity, low corrosiveness, low foam tendency and good viscosity-temperature property.
Description
Technical Field
The invention relates to the technical field of cooling liquid, in particular to a low-conductivity corrosion inhibition cooling liquid and a preparation method thereof.
Background
The coolant is referred to as antifreeze coolant, and is coolant with antifreeze function. The cooling liquid can protect the engine cooling system from being corroded and corroded, effectively inhibit scale formation, prevent the water tank from overheating, and provide lubrication for the water pump thermostat and other components. Is widely used in cooling systems for various automobiles, tractors, internal combustion engine sets, and the like.
The cooling liquid consists of water, antifreezing agent and additive, and is mainly divided into alcohol type cooling liquid, glycerin type cooling liquid and glycol type cooling liquid according to different antifreezing agent components. The alcohol-type cooling liquid is prepared by using ethanol as an antifreezing agent, has low price, good fluidity and simple preparation process, but has lower boiling point, easy evaporation loss, easy rise of freezing point, flammability and the like, and is gradually eliminated; the glycerol type cooling liquid has high boiling point, low volatility, difficult ignition, no toxicity and low corrosiveness, but has poor freezing point reduction effect, high cost and high price; the glycol-type cooling liquid is prepared by using glycol as an antifreezing agent and adding a small amount of additive with defoaming effect and anti-corrosion effect, and because the glycol is easy to dissolve in water, the glycol-type cooling liquid can be prepared into cooling liquids with various freezing points, the lowest freezing point of the cooling liquid can reach-68 ℃, and the glycol-type cooling liquid also has the advantages of high boiling point, low foam tendency, good viscosity temperature and good anti-scaling property, and the cooling liquids used in domestic and foreign engines and sold in the market at present are almost all glycol-type cooling liquids.
However, because glycol in the glycol-type cooling liquid is easy to decompose in use to generate an acidic substance mainly containing acetic acid, corrosion is caused to metals, so that an anticorrosive is required to be added in the production of the hexanediol-type cooling liquid, the conventional anticorrosive is disodium hydrogen phosphate, disodium hydrogen phosphate can react with the acidic substance generated by the glycol-type cooling liquid to reduce the corrosiveness of the glycol-type cooling liquid to metals, but disodium hydrogen phosphate is a strong electrolyte, after the glycol-type cooling liquid is added, the conductivity of the glycol-type cooling liquid is increased, so that the cooling effect of the cooling liquid and the operation efficiency of equipment are affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the low-conductivity corrosion inhibition cooling liquid and the preparation method thereof, and the prepared cooling liquid has low conductivity, low corrosiveness, low foam tendency and good viscosity-temperature property.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the low-conductivity corrosion inhibition cooling liquid comprises the following raw materials in parts by mass: 55-60 parts of deionized water, 40-45 parts of ethylene glycol, 5-5.5 parts of pentaerythritol, 2-2.5 parts of copolymer of chitosan and polyethylene glycol, 0.5-0.6 part of nano particles, 0.5-0.6 part of sebacic acid, 0.5-0.6 part of borax, 0.4-0.5 part of methylbenzotriazole, 0.3-0.4 part of sodium benzoate, 0.3-0.4 part of sodium silicate, 0.3-0.4 part of 2- (sodium-sulfophenyl) ethyl siloxane, 0.1-0.12 part of sodium hydroxide and 0.01-0.02 part of polyether defoamer;
The preparation method of the copolymer of chitosan and polyethylene glycol comprises the following steps: preparing chitosan solution and copolymerizing;
the chitosan solution is prepared, after chitosan and acetic acid solution are mixed, stirring is carried out for 10-20min at room temperature, and chitosan solution is obtained;
in the preparation of the chitosan solution, the mass volume ratio of the chitosan to the acetic acid solution is 22-25g:220-250mL;
the mass concentration of the acetic acid solution is 1.5-2%;
The copolymerization is carried out, after micromolecular hydroxyl polyethylene glycol carboxyl and macromolecular hydroxyl polyethylene glycol carboxyl are mixed with deionized water, stirring is carried out for 20-30min at room temperature, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide are added, stirring is carried out for 20-30min at room temperature, chitosan solution is added, stirring is carried out for 20-22h at room temperature, pH is controlled to 4-5 in the stirring process, a copolymerization product is obtained, and the copolymerization product is dried at 110-120 ℃ to obtain a copolymer of chitosan and polyethylene glycol;
In the copolymerization, the mass volume ratio of the micromolecular hydroxypolyethylene glycol carboxyl, the macromolecular hydroxypolyethylene glycol carboxyl, the deionized water, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the N-hydroxysuccinimide and the chitosan solution is 8-10g:10-12g:130-150mL:3.5-4.3g:2.1-2.6g:230-250mL;
The weight average molecular weight of the chitosan is 50kDa;
The weight average molecular weight of the small molecular hydroxyl polyethylene glycol carboxyl is 1kDa;
the weight average molecular weight of the macromolecular hydroxy polyethylene glycol carboxyl is 5kDa;
The preparation method of the nanoparticle comprises the following steps: cleaning, silane modification and grafting;
The nano copper powder is cleaned by adopting absolute ethyl alcohol, acetone and deionized water in sequence, and then is dried at 110-120 ℃ to obtain cleaned copper powder;
In the cleaning process, the mass volume ratio of the absolute ethyl alcohol to the acetone to the deionized water to the nano copper powder is 2500-3000mL, 2500-3000mL and 50-55g;
the particle size of the nanometer copper powder is 100-200nm;
the silane is modified, 3-aminopropyl trimethoxy silane, absolute ethyl alcohol and deionized water are mixed, stirred at room temperature for 10-20min, washed copper powder is added, stirred at 40-50 ℃ for 7-8h, centrifuged at 7000-8000rpm for 10-15min, the precipitate is washed, and the precipitate is dried at 110-120 ℃ to obtain silane modified copper powder;
In the silane modification, the mass volume ratio of the 3-aminopropyl trimethoxy silane to the absolute ethyl alcohol to the deionized water to the washed copper powder is 50-52g, 900-950mL, 100-150mL and 10-12g;
The grafting is carried out, after silane modified copper powder, ethylenediamine tetraacetic anhydride and N, N-dimethylformamide are mixed, stirring is carried out for 20-24h at 70-75 ℃, centrifugation is carried out for 10-15min at a speed of 7000-8000rpm, after sediment is cleaned, the sediment is dried at 110-120 ℃ to obtain nano particles;
in the grafting, the mass volume ratio of the silane modified copper powder, the ethylenediamine tetraacetic anhydride and the N, N-dimethylformamide is 10-13g to 20-25g to 3500-4000mL;
The preparation method of the low-conductivity corrosion inhibition cooling liquid comprises the steps of weighing raw materials according to the specified parts by weight, mixing sodium benzoate and deionized water, stirring for 10-20min at room temperature, adding ethylene glycol, pentaerythritol and sebacic acid, stirring for 10-20min at room temperature, adding borax, methylbenzotriazole, sodium silicate, 2- (sodium-sulfophenyl) ethyl siloxane and polyether defoamer, continuously stirring for 80-100min at room temperature, adding sodium hydroxide, continuously stirring for 30-40min at room temperature, adding copolymer of chitosan and polyethylene glycol and nano particles, and continuously stirring for 30-40min at room temperature to obtain the low-conductivity corrosion inhibition cooling liquid.
Compared with the prior art, the invention has the beneficial effects that:
(1) The low-conductivity corrosion inhibition cooling liquid is added with the copolymer of chitosan and polyethylene glycol and nano particles. Wherein, the copolymer of chitosan and polyethylene glycol is a dendrimer, specifically, chitosan is taken as a main chain, and polyethylene glycol with different molecular weights is taken as a side chain; when preparing the copolymer of chitosan and polyethylene glycol, polyethylene glycol with different molecular weights is grafted on the chitosan through the reaction of amino groups on the chitosan and carboxyl groups on the carboxyl groups of the hydroxyl polyethylene glycol; wherein, macromolecular polyethylene glycol can play a role in improving the adhesiveness of the copolymer of chitosan and polyethylene glycol, small molecular polyethylene glycol can play a role in improving the lubricity of the copolymer of chitosan and polyethylene glycol, after the copolymer of chitosan and polyethylene glycol is added into cooling liquid, part of the copolymer of chitosan and polyethylene glycol can be adhered to the surface of an engine in the process of forming a film by methylbenzotriazole, so that the film forming can be promoted, and the other part of the copolymer of chitosan and polyethylene glycol can promote the flow of the cooling liquid and improve the adhesiveness; the unreacted amino on the copolymer of chitosan and polyethylene glycol can also be combined with hydrogen ions on acidic substances generated by ethylene glycol, so that the corrosiveness of the cooling liquid is reduced; the existence of the copolymer of chitosan and polyethylene glycol can also reduce the transmission of ions in the cooling liquid, thereby reducing the conductivity of the cooling liquid; in addition, the polyethylene glycol in the copolymer of chitosan and polyethylene glycol can also inhibit the generation of foam, thereby reducing the foam tendency of the cooling liquid. The nanometer particle is nanometer copper powder grafted with ethylenediamine tetraacetic acid dianhydride, when preparing nanometer particle, firstly silane modification is carried out on the cleaned copper powder, aminopropyl is grafted on the surface of the copper powder, then ethylenediamine tetraacetic acid dianhydride is added to react with the aminopropyl, and ethylenediamine tetraacetic acid is grafted on the surface of the copper powder, thus obtaining nanometer particle; the copper powder in the nano particles can improve the heat dissipation effect of the cooling liquid, and the introduction of ethylenediamine tetraacetic acid diamine can reduce the aggregation of the copper powder and improve the fluidity of the copper powder, so that the dispersion of the copper powder in the cooling liquid is promoted and the viscosity-temperature property of the cooling liquid is improved; the ethylenediamine tetraacetic acid diamine can also complex corroded metal ions and reduce the transmission of ions in the cooling liquid, thereby reducing the conductivity of the cooling liquid; in addition, ungrafted amino on the surface of the nanoparticle can be combined with hydrogen ions in acidic substances generated by ethylene glycol, copper powder can also react with the acidic substances generated by ethylene glycol to generate copper ions, so that the corrosion to the surface of an engine is reduced, and the corrosiveness of cooling liquid is reduced;
(2) The electric conductivity of the cooling liquid is low, and the electric conductivity is 4.1-4.7 mu S/cm;
(3) The coolant provided by the invention has low corrosiveness, and is tested according to an SH/T0085-1991 engine coolant corrosion assay, wherein the mass change of a red copper test piece is-0.8 mg to-0.5 mg, the mass change of a tin test piece is-2.1 mg to-1.6 mg, the mass change of a brass test piece is-1.2 mg to-0.8 mg, the mass change of a cast steel test piece is +0.5mg to +0.8mg, the mass change of a cast iron test piece is +0.5mg to +0.8mg, and the mass change of a cast aluminum test piece is-3.5 mg to-2.9 mg;
(4) The cooling liquid has low foam tendency, the foam volume is 38-42mL, and the foam disappearance time is 1.8-2.1s according to the test of SH/T0066-2002 engine cooling liquid foam tendency measurement method;
(5) The cooling liquid of the invention has good viscosity-temperature property, the viscosity at the temperature of minus 20 ℃ is 88.2-94.5 mPas, the viscosity at the temperature of 0 ℃ is 42.0-46.3 mPas, and the viscosity at the temperature of 25 ℃ is 22.5-24.6 mPas.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The low-conductivity corrosion inhibition cooling liquid comprises the following raw materials in parts by mass: 55 parts of deionized water, 40 parts of ethylene glycol, 5 parts of pentaerythritol, 2 parts of a copolymer of chitosan and polyethylene glycol, 0.5 part of nano particles, 0.5 part of sebacic acid, 0.5 part of borax, 0.4 part of methylbenzotriazole, 0.3 part of sodium benzoate, 0.3 part of sodium silicate, 0.3 part of 2- (sodium-sulfophenyl) ethyl siloxane, 0.1 part of sodium hydroxide and 0.01 part of polyether defoamer;
the preparation method of the copolymer of chitosan and polyethylene glycol specifically comprises the following steps:
1. Preparing chitosan solution: mixing 22g of chitosan with 220mL of acetic acid solution with the mass concentration of 1.5%, and stirring for 10min at room temperature to obtain chitosan solution;
2. copolymerization: mixing 8g of small molecular hydroxyl polyethylene glycol carboxyl, 10g of large molecular hydroxyl polyethylene glycol carboxyl and 130mL of deionized water, stirring at room temperature for 20min, adding 3.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, adding 2.1g N-hydroxysuccinimide, continuously stirring at room temperature for 20min, adding 230mL of chitosan solution, continuously stirring at room temperature for 20h, controlling the pH to 4 in the stirring process, obtaining a copolymerization product, and drying the copolymerization product at 110 ℃ to obtain a copolymer of chitosan and polyethylene glycol;
The weight average molecular weight of the chitosan is 50kDa;
The weight average molecular weight of the small molecular hydroxyl polyethylene glycol carboxyl is 1kDa;
the weight average molecular weight of the macromolecular hydroxy polyethylene glycol carboxyl is 5kDa;
the preparation method of the nanoparticle comprises the following steps:
1. Cleaning: washing 50g of nano copper powder by sequentially adopting 2500mL of absolute ethyl alcohol, 2500mL of acetone and 2500mL of deionized water, and then drying at 110 ℃ to obtain washed copper powder;
the particle size of the nanometer copper powder is 100nm;
2. Silane modification: 50g of 3-aminopropyl trimethoxysilane, 900mL of absolute ethyl alcohol and 100mL of deionized water are mixed, stirred at room temperature for 10min, 10g of washed copper powder is added, stirred at 40 ℃ for 7h, centrifuged at 7000rpm for 10min, 300mL of absolute ethyl alcohol and 300mL of deionized water are sequentially adopted to wash the precipitate, and the precipitate is dried at 110 ℃ to obtain silane modified copper powder;
3. Grafting: after 10g of silane modified copper powder, 20g of ethylenediamine tetraacetic acid dianhydride and 2500 mL of N, N-dimethylformamide are mixed, stirred at 70 ℃ for 20h, centrifuged at 7000rpm for 10-15min, 300mL of N, N-dimethylformamide, 300mL of saturated sodium bicarbonate solution and 300mL of deionized water are sequentially adopted to clean the precipitate, and the precipitate is dried at 110 ℃ to obtain the nano particles.
The embodiment also provides a preparation method of the low-conductivity corrosion inhibition cooling liquid, which comprises the following steps:
Weighing raw materials according to the specified parts by weight, mixing sodium benzoate and deionized water, stirring for 10min at room temperature, adding ethylene glycol, pentaerythritol and sebacic acid, stirring for 10min at room temperature, adding borax, methyl benzotriazole, sodium silicate, 2- (sodium-sulfophenyl) ethyl siloxane and polyether defoamer, continuously stirring for 80min at room temperature, adding sodium hydroxide, continuously stirring for 30min at room temperature, adding copolymer of chitosan and polyethylene glycol and nano particles, and continuously stirring for 30min at room temperature to obtain the low-conductivity corrosion inhibition cooling liquid.
Example 2
The low-conductivity corrosion inhibition cooling liquid comprises the following raw materials in parts by mass: 58 parts of deionized water, 42 parts of ethylene glycol, 5.2 parts of pentaerythritol, 2.2 parts of a copolymer of chitosan and polyethylene glycol, 0.55 parts of nano particles, 0.5 part of sebacic acid, 0.5 part of borax, 0.5 part of methylbenzotriazole, 0.3 part of sodium benzoate, 0.3 part of sodium silicate, 0.3 part of 2- (sodium-sulfophenyl) ethyl siloxane, 0.11 part of sodium hydroxide and 0.01 part of polyether defoamer;
the preparation method of the copolymer of chitosan and polyethylene glycol specifically comprises the following steps:
1. Preparing chitosan solution: mixing 23g of chitosan with 230mL of acetic acid solution with mass concentration of 1.8%, and stirring at room temperature for 15min to obtain chitosan solution;
2. Copolymerization: mixing 9g of small molecular hydroxyl polyethylene glycol carboxyl, 11g of large molecular hydroxyl polyethylene glycol carboxyl and 140mL of deionized water, stirring at room temperature for 25min, adding 4g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 2.4g N-hydroxysuccinimide, continuing stirring at room temperature for 25min, adding 240mL of chitosan solution, continuing stirring at room temperature for 21h, controlling the pH value to 4.5 in the stirring process, obtaining a copolymerization product, and drying the copolymerization product at 115 ℃ to obtain a copolymer of chitosan and polyethylene glycol;
The weight average molecular weight of the chitosan is 50kDa;
The weight average molecular weight of the small molecular hydroxyl polyethylene glycol carboxyl is 1kDa;
the weight average molecular weight of the macromolecular hydroxy polyethylene glycol carboxyl is 5kDa;
the preparation method of the nanoparticle comprises the following steps:
1. Cleaning: sequentially cleaning 52g of nano copper powder by 2800mL of absolute ethyl alcohol, 2800mL of acetone and 2800mL of deionized water, and then drying at 115 ℃ to obtain cleaned copper powder;
the particle size of the nanometer copper powder is 100nm;
2. Silane modification: 51g of 3-aminopropyl trimethoxysilane, 920mL of absolute ethyl alcohol and 120mL of deionized water are mixed, stirred at room temperature for 15min, 11g of cleaned copper powder is added, stirred at 45 ℃ for 7.5h, centrifuged at 7500rpm for 12min, 320mL of absolute ethyl alcohol and 320mL of deionized water are sequentially adopted to clean the precipitate, and the precipitate is dried at 115 ℃ to obtain silane modified copper powder;
3. Grafting: 12g of silane modified copper powder, 23g of ethylenediamine tetraacetic anhydride and 380 mL of N, N-dimethylformamide are mixed, stirred at 72 ℃ for 22h, centrifuged at 7500rpm for 12min, 320mL of N, N-dimethylformamide, 320mL of saturated sodium bicarbonate solution and 320mL of deionized water are sequentially adopted to clean the precipitate, and the precipitate is dried at 115 ℃ to obtain the nano particles.
The embodiment also provides a preparation method of the low-conductivity corrosion inhibition cooling liquid, which comprises the following steps:
Weighing raw materials according to the specified parts by weight, mixing sodium benzoate and deionized water, stirring for 15min at room temperature, adding ethylene glycol, pentaerythritol and sebacic acid, stirring for 15min at room temperature, adding borax, methyl benzotriazole, sodium silicate, 2- (sodium-sulfophenyl) ethyl siloxane and polyether defoamer, continuously stirring for 90min at room temperature, adding sodium hydroxide, continuously stirring for 35min at room temperature, adding copolymer of chitosan and polyethylene glycol and nano particles, and continuously stirring for 35min at room temperature to obtain the low-conductivity corrosion inhibition cooling liquid.
Example 3
The low-conductivity corrosion inhibition cooling liquid comprises the following raw materials in parts by mass: 60 parts of deionized water, 45 parts of ethylene glycol, 5.5 parts of pentaerythritol, 2.5 parts of a copolymer of chitosan and polyethylene glycol, 0.6 part of nano particles, 0.6 part of sebacic acid, 0.6 part of borax, 0.5 part of methylbenzotriazole, 0.4 part of sodium benzoate, 0.4 part of sodium silicate, 0.4 part of 2- (sodium-sulfophenyl) ethyl siloxane, 0.12 part of sodium hydroxide and 0.02 part of polyether defoamer;
the preparation method of the copolymer of chitosan and polyethylene glycol specifically comprises the following steps:
1. Preparing chitosan solution: mixing 25g of chitosan with 250mL of acetic acid solution with mass concentration of 2%, and stirring at room temperature for 20min to obtain chitosan solution;
2. copolymerization: mixing 10g of small molecular hydroxyl polyethylene glycol carboxyl, 12g of macromolecular hydroxyl polyethylene glycol carboxyl and 150mL of deionized water, stirring at room temperature for 30min, adding 4.3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, adding 2.6g N-hydroxysuccinimide, continuously stirring at room temperature for 30min, adding 250mL of chitosan solution, continuously stirring at room temperature for 22h, controlling the pH to 5 in the stirring process, obtaining a copolymerization product, and drying the copolymerization product at 120 ℃ to obtain a copolymer of chitosan and polyethylene glycol;
The weight average molecular weight of the chitosan is 50kDa;
The weight average molecular weight of the small molecular hydroxyl polyethylene glycol carboxyl is 1kDa;
the weight average molecular weight of the macromolecular hydroxy polyethylene glycol carboxyl is 5kDa;
the preparation method of the nanoparticle comprises the following steps:
1. cleaning: sequentially cleaning 55g of nano copper powder by using 3000mL of absolute ethyl alcohol, 3000mL of acetone and 3000mL of deionized water, and then drying at 120 ℃ to obtain cleaned copper powder;
the particle size of the nanometer copper powder is 200nm;
2. Silane modification: 52g of 3-aminopropyl trimethoxysilane, 950mL of absolute ethyl alcohol and 150mL of deionized water are mixed, stirred at room temperature for 20min, 12g of cleaned copper powder is added, stirred at 50 ℃ for 8h, centrifuged at 8000rpm for 15min, and after the sediment is cleaned by 350mL of absolute ethyl alcohol and 350mL of deionized water in sequence, the sediment is dried at 120 ℃ to obtain silane modified copper powder;
3. Grafting: 13g of silane modified copper powder, 25g of ethylenediamine tetraacetic anhydride and 4000mL of N, N-dimethylformamide are mixed, stirred at 75 ℃ for 24 hours, centrifuged at 8000rpm for 15 minutes, and 350mL of N, N-dimethylformamide, 350mL of saturated sodium bicarbonate solution and 350mL of deionized water are sequentially used for cleaning the precipitate, and the precipitate is dried at 120 ℃ to obtain the nano particles.
The embodiment also provides a preparation method of the low-conductivity corrosion inhibition cooling liquid, which comprises the following steps:
Weighing raw materials according to the specified parts by weight, mixing sodium benzoate and deionized water, stirring at room temperature for 20min, adding ethylene glycol, pentaerythritol and sebacic acid, stirring at room temperature for 20min, adding borax, methyl benzotriazole, sodium silicate, 2- (sodium-sulfophenyl) ethyl siloxane and polyether defoamer, continuously stirring at room temperature for 100min, adding sodium hydroxide, continuously stirring at room temperature for 40min, adding copolymer of chitosan and polyethylene glycol and nano particles, and continuously stirring at room temperature for 40min to obtain the low-conductivity corrosion inhibition cooling liquid.
Comparative example 1
The technical scheme of the comparative example is that the preparation is carried out on the basis of the embodiment 2, the preparation is that the copolymer of chitosan and polyethylene glycol is omitted from the raw materials of the low-conductivity corrosion-inhibiting cooling liquid, the addition of the copolymer of chitosan and polyethylene glycol is correspondingly omitted in the preparation of the low-conductivity corrosion-inhibiting cooling liquid, and the rest of the operations are the same as the embodiment 2.
Comparative example 2
The technical scheme of the comparative example is that the adjustment is carried out on the basis of the embodiment 2, the adjustment is that nano copper powder with the grain diameter of 100nm is used for replacing nano particles in the raw materials of the low-conductivity corrosion inhibition cooling liquid, and correspondingly nano copper powder with the grain diameter of 100nm is used for replacing nano particles in the preparation of the low-conductivity corrosion inhibition cooling liquid, and the rest operation is the same as the embodiment 2.
Test example 1
The electrical conductivities of the cooling fluids prepared in examples 1-3 and comparative examples 1-2 were tested and the test results were as follows:
test example 2
The corrosiveness of the coolant solutions prepared in examples 1-3 and comparative examples 1-2 were tested according to the SH/T0085-1991 engine coolant corrosion assay, and the test results are as follows:
test example 3
The cooling fluids prepared in examples 1-3 and comparative examples 1-2 were tested for foam volume, foam disappearance time according to the SH/T0066-2002 engine coolant foam tendency assay, and the test results are as follows:
test example 4
The viscosity-temperature properties of the cooling fluids prepared in examples 1 to 3 and comparative examples 1 to 2 were measured, specifically, the viscosity of the cooling fluids at-20℃and 0℃and 25℃were measured, respectively, and the measurement results were as follows:
from the results of test examples 1 to 4, it can be seen that the addition of the copolymer of chitosan and polyethylene glycol can reduce the conductivity, corrosiveness, foam tendency and improve the viscosity-temperature property; by adding the nano particles, the conductivity and corrosiveness can be reduced, and the viscosity-temperature property can be improved.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The low-conductivity corrosion inhibition cooling liquid is characterized by comprising the following raw materials in parts by mass: 55-60 parts of deionized water, 40-45 parts of ethylene glycol, 5-5.5 parts of pentaerythritol, 2-2.5 parts of copolymer of chitosan and polyethylene glycol, 0.5-0.6 part of nano particles, 0.5-0.6 part of sebacic acid, 0.5-0.6 part of borax, 0.4-0.5 part of methylbenzotriazole, 0.3-0.4 part of sodium benzoate, 0.3-0.4 part of sodium silicate, 0.3-0.4 part of 2- (sodium-sulfophenyl) ethyl siloxane, 0.1-0.12 part of sodium hydroxide and 0.01-0.02 part of polyether defoamer;
The preparation method of the copolymer of chitosan and polyethylene glycol comprises the following steps: preparing chitosan solution and copolymerizing;
The copolymerization is carried out, after micromolecular hydroxyl polyethylene glycol carboxyl and macromolecular hydroxyl polyethylene glycol carboxyl are mixed with deionized water, stirring is carried out at room temperature, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is added, stirring is carried out at room temperature continuously, chitosan solution is added, stirring is carried out at room temperature continuously, pH is controlled to 4-5 in the stirring process, a copolymerization product is obtained, and the copolymerization product is dried, thus obtaining a copolymer of chitosan and polyethylene glycol;
in the copolymerization, the weight average molecular weight of the chitosan is 50kDa;
The weight average molecular weight of the small molecular hydroxyl polyethylene glycol carboxyl is 1kDa;
the weight average molecular weight of the macromolecular hydroxy polyethylene glycol carboxyl is 5kDa;
The preparation method of the nanoparticle comprises the following steps: cleaning, silane modification and grafting;
The silane is modified, 3-aminopropyl trimethoxy silane, absolute ethyl alcohol and deionized water are mixed and stirred at room temperature, copper powder after cleaning is added, stirring is carried out at 40-50 ℃, centrifugation is carried out, and precipitate is cleaned and dried, thus obtaining silane modified copper powder;
and (3) the grafting is carried out, after silane modified copper powder, ethylenediamine tetraacetic anhydride and N, N-dimethylformamide are mixed, stirring is carried out at 70-75 ℃, centrifugation is carried out, and the precipitate is washed and dried, thus obtaining the nano particles.
2. The low-conductivity corrosion inhibition cooling liquid according to claim 1, wherein the chitosan solution is prepared, and the chitosan solution is obtained by mixing chitosan with acetic acid solution and stirring at room temperature;
in the preparation of the chitosan solution, the mass volume ratio of the chitosan to the acetic acid solution is 22-25g:220-250mL;
the mass concentration of the acetic acid solution is 1.5-2%.
3. The low-conductivity corrosion inhibition cooling liquid according to claim 1, wherein in the copolymerization, the mass volume ratio of the small molecular hydroxyl polyethylene glycol carboxyl, the large molecular hydroxyl polyethylene glycol carboxyl, deionized water, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and chitosan solution is 8-10g:10-12g:130-150mL:3.5-4.3g:2.1-2.6g:230-250mL.
4. The low-conductivity corrosion inhibition cooling liquid according to claim 1, wherein the washing is carried out by washing nano copper powder with absolute ethyl alcohol, acetone and deionized water in sequence, and then drying to obtain washed copper powder;
In the cleaning process, the mass volume ratio of the absolute ethyl alcohol to the acetone to the deionized water to the nano copper powder is 2500-3000mL, 2500-3000mL and 50-55g;
The particle size of the nanometer copper powder is 100-200nm.
5. The low-conductivity corrosion inhibition cooling liquid according to claim 1, wherein in the silane modification, the mass-volume ratio of 3-aminopropyl trimethoxysilane, absolute ethyl alcohol, deionized water and washed copper powder is 50-52g:900-950ml:100-150ml:10-12g.
6. The low conductivity corrosion inhibition coolant according to claim 1, wherein in the grafting, the mass-volume ratio of the silane modified copper powder, the ethylenediamine tetraacetic acid dianhydride and the N, N-dimethylformamide is 10-13g:20-25g:3500-4000mL.
7. A method for preparing the low-conductivity corrosion inhibition cooling liquid according to any one of claims 1-6, which is characterized in that raw materials are weighed according to specified parts by weight, sodium benzoate and deionized water are mixed, and then are stirred at room temperature, ethylene glycol, pentaerythritol and sebacic acid are added, and then are stirred at room temperature, borax, methylbenzotriazole, sodium silicate, 2- (sodium-sulfophenyl) ethyl siloxane and polyether defoamer are added, and then are continuously stirred at room temperature, sodium hydroxide is added, and then are continuously stirred at room temperature, and then copolymers and nano particles of chitosan and polyethylene glycol are added, and finally are continuously stirred at room temperature, so that the low-conductivity corrosion inhibition cooling liquid is obtained.
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| CN101948676A (en) * | 2010-08-30 | 2011-01-19 | 蓝星环境工程有限公司 | High reserve alkalinity engine cooling liquid |
| CN107142091A (en) * | 2017-06-30 | 2017-09-08 | 北京雅士科莱恩石油化工有限公司 | A kind of full stress-strain type nanometer anti-icing fluid and preparation method thereof |
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| CN114621735B (en) * | 2020-12-14 | 2023-05-30 | 中国石油化工股份有限公司 | Drilling fluid hydration type lubricant and preparation method and application thereof |
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| CN101948676A (en) * | 2010-08-30 | 2011-01-19 | 蓝星环境工程有限公司 | High reserve alkalinity engine cooling liquid |
| CN107142091A (en) * | 2017-06-30 | 2017-09-08 | 北京雅士科莱恩石油化工有限公司 | A kind of full stress-strain type nanometer anti-icing fluid and preparation method thereof |
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