CN113913801B - Organic-inorganic hybridization-based waste heat black liquor - Google Patents
Organic-inorganic hybridization-based waste heat black liquor Download PDFInfo
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- CN113913801B CN113913801B CN202111270493.7A CN202111270493A CN113913801B CN 113913801 B CN113913801 B CN 113913801B CN 202111270493 A CN202111270493 A CN 202111270493A CN 113913801 B CN113913801 B CN 113913801B
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- 239000002918 waste heat Substances 0.000 title claims abstract description 31
- 238000009396 hybridization Methods 0.000 title claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 19
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- -1 methacryloxypropyl Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 229920000178 Acrylic resin Polymers 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000004945 emulsification Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000012530 fluid Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000012224 working solution Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical group [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- HEQBUZNAOJCRSL-UHFFFAOYSA-N iron(ii) chromite Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Fe+3] HEQBUZNAOJCRSL-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a waste heat black liquor based on organic-inorganic hybridization, which is polyacrylic resin emulsion containing cage polysilsesquioxane groups; the polyacrylic resin emulsion is obtained by copolymerization and emulsification of a modified material containing cage polysilsesquioxane groups and acrylic resin. The blackening liquid greatly improves the corrosion resistance of the workpiece after blackening, and the salt fog resistance time of the workpiece after the waste heat blackening liquid is adopted for treatment reaches 96 hours; the heat resistance of the black liquor is greatly improved, and the resin in the black liquor is not decomposed by heating under the impact of a high-temperature workpiece at 400-500 ℃, so that the black liquor can be applied to the black liquor treatment of a medium-high-temperature workpiece.
Description
Technical Field
The invention relates to a waste heat black liquor based on organic-inorganic hybridization.
Background
The blackening process is to form a compact black protective film layer on the surface of a metal workpiece by a physical or chemical method, so that the rust resistance of the workpiece is enhanced, and the appearance of the workpiece is beautified. According to the different film forming principles, the blackening process can be divided into oxidation blackening, normal temperature blackening, phosphorization blackening and waste heat blackening.
The principle of the waste heat blackening technology is that waste heat of a workpiece in the heat treatment or other processing processes is utilized, so that a black high polymer resin film layer which is firmly combined and is not easy to fall off is formed on the surface of the steel workpiece at the moment of contacting with blackening liquid. The process is simple and easy to operate, does not require thorough oil and rust removal before blackening of the workpiece, has high production efficiency, is suitable for flow line production, and has long ageing period of the bath solution, strong film adhesion and uniform color. The existing work piece after the waste heat blackening treatment has good corrosion resistance, the salt fog resistance time is 24 hours, but in the actual use process, the long-term corrosion resistance requirement of the work piece outdoors still cannot be met.
Disclosure of Invention
The invention aims to: the invention aims to provide waste heat blackening liquid which can meet the long-term outdoor corrosion prevention requirement of a blackened workpiece.
The technical scheme is as follows: the waste heat black liquor based on organic-inorganic hybridization is polyacrylic resin emulsion containing cage polysilsesquioxane groups.
Wherein the polyacrylic resin emulsion is obtained by hybridization of a modified material containing cage polysilsesquioxane groups and acrylic resin.
The specific preparation method of the polyacrylic resin emulsion comprises the following steps: weighing a certain amount of monomer 1 (the monomer 1 is MMA and methyl methacrylate), adding monomer 2 (the monomer 2 is methacryloxypropyl heptaisobutyl-POSS, abbreviated as MA7 iBu-POSS) into the monomer 1 according to 20-25% of the monomer 1, adding an emulsifying agent accounting for 5% of the monomer 1 and water accounting for 30-50% of the monomer 1, performing ultrasonic dispersion, mechanically stirring to uniformly mix, heating in an oil bath to obtain a monomer emulsified solution, dropwise adding an initiator solution accounting for 0.2% of the monomer 1 into the solution, gradually heating to 70-80 ℃, and reacting for 6-7 hours to obtain a copolymer emulsified solution.
The reaction equation is as follows:
wherein the molar ratio of n to m is 5:1 to 9:1.
wherein, R groups on the cage polysilsesquioxane groups are phenyl, hydroxyl, amino or fluoroalkyl groups; the phenyl can improve the heat resistance of the film; fluoroalkyl groups can improve the hydrophobic properties of the film.
The structural formula of the cage polysilsesquioxane group (POSS) is as follows:
wherein the acrylic resin of the polyacrylic resin emulsion is methyl methacrylate.
The waste heat black liquor also comprises water-based color paste, wherein the pigment used by the water-based color paste is one of carbon black, iron oxide black, chrome black or aniline black, and the addition amount of the water-based color paste is 1-15% of the mass of the polyacrylic resin emulsion.
When the hardness and the brightness of a blackening film on the surface of a workpiece need to be regulated, adding aqueous resin into the residual heat blackening liquid, wherein the aqueous resin is styrene-acrylic emulsion or acrylic emulsion. When other functional resins are introduced into the system, the R group in the POSS-R group can react with the functional groups of other functional resins in the curing process, so that a cross-linked three-dimensional network structure is formed, and the adhesion and combination capacity of the black liquor and the base material can be enhanced.
Wherein, the adding mass ratio of the water-based resin to the polyacrylic resin emulsion is 5-15: 30-10.
Wherein the waste heat black liquor also comprises a bactericide and/or a defoamer; the bactericide is sodium benzoate; the defoaming agent is polyether defoaming agent or organic silicon defoaming agent.
After the workpiece to be treated is heated, the workpiece is directly brought into blackening liquid by continuous conveying equipment and is taken out within a certain time, an organic-inorganic hybrid nano blackening film which has good corrosion resistance, strong coverage and firm combination and hydrophobic surface is formed on the surface of the workpiece, and the blackening workpiece containing the blackening film is kept for 96 hours without rust corrosion according to a 5% neutral salt spray test method specified in GB/T10125.
According to the invention, the POSS group is introduced into the acrylic main chain, namely a large number of silica structures are introduced into the acrylic main chain, so that the hydrophobic property of the acrylic resin can be greatly improved, and the aim of improving the corrosion resistance of the base material is fulfilled. The principle of blackening the organic-inorganic hybrid resin is as follows: immersing the workpiece in the waste heat black liquor containing the organic/inorganic hybrid nano component by utilizing the residual heat carried by the workpiece in the previous working procedure, continuously and uniformly depositing the organic/inorganic hybrid nano component on the surface of the workpiece under the action of high-temperature waste heat carried by the workpiece to form a compact organic/inorganic hybrid hydrophobic black film layer, wherein the surface of the black film has hydrophobic characteristic due to hydrophobic groups in the film structure, and the corrosion resistance is greatly improved; meanwhile, the modified acrylic resin has better heat resistance, can be applied to blackening treatment of a workpiece at medium and high temperature, and can not be decomposed by heating under the impact of the workpiece at the high temperature of 500 ℃ so as to ensure blackening effect.
The beneficial effects are that: compared with the existing waste heat black liquor, the invention has the remarkable advantages that: (1) The corrosion resistance of the workpiece after blackening is greatly improved, and the salt spray resistance time of the workpiece after the waste heat blackening liquid treatment reaches 96 hours; (2) The heat resistance of the black liquor is greatly improved, and the resin in the black liquor is not decomposed by heating under the impact of a high-temperature workpiece at 400-500 ℃, so that the black liquor can be applied to the black liquor treatment of a medium-high-temperature workpiece.
Drawings
FIG. 1 is an appearance of a workpiece treated with the working fluid of example 1% for 96 hours;
FIG. 2 is an appearance of a workpiece treated with the working fluid of example 2 at 13% for 96 hours;
FIG. 3 is an appearance of a workpiece treated with the working fluid of example 3 at 13% for 96 hours;
FIG. 4 is an appearance of a workpiece treated with the working fluid of comparative example 1 at 13% for 50 hours;
FIG. 5 is an appearance of a blackening film obtained by immersing a steel work piece at 500℃in the working liquid of example 1% in water;
FIG. 6 is an appearance of a blackening film obtained by immersing a steel work piece at 500℃in the working liquid of example 2% at 13%;
FIG. 7 is an appearance of a blackening film obtained by immersing a steel work piece at 500℃in the working liquid of example 3% by weight;
FIG. 8 is a view showing the appearance of a blackening film obtained by immersing a steel work piece at 500℃in the working liquid of comparative example 1% at 13%.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
The invention relates to a waste heat black liquor based on organic-inorganic hybridization, which is prepared by the following steps: 50 parts of cage polysilsesquioxane modified polyacrylic resin emulsion (wherein R groups in a POSS structure are fluoroalkyl), 0.5 part of water-based nanometer black color paste and 1 part of sodium benzoate are mixed and uniformly stirred to obtain waste heat black liquor.
Example 2
The invention relates to a waste heat black liquor based on organic-inorganic hybridization, which is prepared by the following steps: 30 parts of a cage polysilsesquioxane modified polyacrylic resin emulsion (wherein the R group in the POSS structure is-NH) 2 ) Mixing 5 parts of styrene-acrylic emulsion, 1 part of aqueous black color paste and 0.5 part of polyether defoamer, and uniformly stirring to obtain waste heat black liquor.
Example 3
The invention relates to a waste heat black liquor based on organic-inorganic hybridization, which is prepared by the following steps: 10 parts of cage polysilsesquioxane modified polyacrylic resin emulsion (wherein R groups in a POSS structure are phenyl groups), 15 parts of pure acrylic emulsion, 1.5 parts of aqueous black color paste and 0.5 part of organic silicon defoamer are mixed and uniformly stirred to obtain waste heat black liquor.
Comparative example 1
The waste heat black liquor is prepared by the following method: mixing 30 parts of polyacrylic resin emulsion, 5 parts of styrene-acrylic emulsion, 1 part of aqueous black color paste and 0.5 part of polyether defoamer, and uniformly stirring to obtain waste heat black liquor.
The waste heat-treated black liquor (stock solution) of examples 1 to 3 and the waste heat-treated black liquor of comparative example 1 were diluted with water to obtain solutions (working solutions) having a mass fraction of 13%, respectively.
Performance tests were performed on 13% working solutions prepared from the blackening solutions of examples 1 to 3 and comparative example 1, respectively:
immersing the steel workpiece with the temperature of 400 ℃ into the prepared 13% working solution, taking out the workpiece after 30 seconds, drying the workpiece by hot air, or airing the workpiece in the air, and forming a waste heat blackening film layer on the surface of the workpiece. The workpiece was subjected to 5% neutral salt spray test method prescribed in GB/T10125, and the change of the surface thereof was observed. As shown in fig. 1 to 4, the workpieces of examples 1 to 3 were kept for 96 hours without rusting, and the workpiece of comparative example 1 began to be rusted beyond 48 hours.
Immersing the steel workpiece with the temperature of 500 ℃ into the prepared 13% working solution, taking out the workpiece after 30 seconds, drying the workpiece by hot air, or airing the workpiece in the air, and forming a waste heat blackening film layer on the surface of the workpiece. As shown in fig. 5 to 8, the work pieces of examples 1 to 3 were formed with blackening films which were completely covered and firmly bonded, indicating that the resin was not decomposed by heat at high temperature; comparative example 1 the blackening film on the work piece surface was incomplete, indicating that the blackening film was decomposed by heat during formation of the resin, failed to firmly bond to the work piece surface, and peeled off.
Claims (1)
1. The waste heat black liquor based on organic-inorganic hybridization is characterized by being prepared by the following steps: 10 parts of cage polysilsesquioxane modified polyacrylic resin emulsion, 15 parts of pure acrylic emulsion, 1.5 parts of water-based black color paste and 0.5 part of organic silicon defoamer are mixed and uniformly stirred to obtain waste heat black liquor;
the preparation method of the polyacrylic resin emulsion comprises the following steps: weighing monomer 1 methyl methacrylate, adding monomer 2 into the monomer 1 according to 20-25% of the mass of the monomer 1, and then adding an emulsifier and water accounting for 5% of the mass of the monomer 1, wherein the addition amount of the water is 30-50% of the mass of the monomer 1; ultrasonic dispersing, mechanical stirring until the mixture is uniform, heating in an oil bath to obtain a monomer emulsified solution, dropwise adding an initiator solution with the mass of 0.2% of that of the monomer into the monomer emulsified solution, gradually heating to 70-80 ℃, and reacting for 6-7 hours to obtain a copolymer emulsified solution; wherein, the monomer 2 is methacryloxypropyl heptaisobutyl-POSS;
wherein, the structural formula of POSS is:
the R group in the POSS structure is phenyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111270493.7A CN113913801B (en) | 2021-10-29 | 2021-10-29 | Organic-inorganic hybridization-based waste heat black liquor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111270493.7A CN113913801B (en) | 2021-10-29 | 2021-10-29 | Organic-inorganic hybridization-based waste heat black liquor |
Publications (2)
| Publication Number | Publication Date |
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| CN113913801A CN113913801A (en) | 2022-01-11 |
| CN113913801B true CN113913801B (en) | 2024-03-22 |
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| CN202111270493.7A Active CN113913801B (en) | 2021-10-29 | 2021-10-29 | Organic-inorganic hybridization-based waste heat black liquor |
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| CN117721451A (en) * | 2023-12-13 | 2024-03-19 | 江苏甬怡紧固件有限公司 | Organic blackening oil and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199262A (en) * | 2011-04-12 | 2011-09-28 | 厦门大学 | Polyhedral oligomeric silsesquioxane amphiphilic block copolymer and preparation method thereof |
| CN105001733A (en) * | 2015-08-14 | 2015-10-28 | 兰州科天环保节能科技有限公司 | Super-hydrophobic outdoor water-borne wood coating and preparation method thereof |
| CN106947030A (en) * | 2017-03-27 | 2017-07-14 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersions and preparation method and application |
| CN108300173A (en) * | 2018-02-07 | 2018-07-20 | 东南大学 | A kind of steel surface low temperature exhaust heat blackening agent for surface and its methods for making and using same |
-
2021
- 2021-10-29 CN CN202111270493.7A patent/CN113913801B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199262A (en) * | 2011-04-12 | 2011-09-28 | 厦门大学 | Polyhedral oligomeric silsesquioxane amphiphilic block copolymer and preparation method thereof |
| CN105001733A (en) * | 2015-08-14 | 2015-10-28 | 兰州科天环保节能科技有限公司 | Super-hydrophobic outdoor water-borne wood coating and preparation method thereof |
| CN106947030A (en) * | 2017-03-27 | 2017-07-14 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersions and preparation method and application |
| CN108300173A (en) * | 2018-02-07 | 2018-07-20 | 东南大学 | A kind of steel surface low temperature exhaust heat blackening agent for surface and its methods for making and using same |
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