CN114702875A - Waterborne polyurethane scale-inhibiting coating and preparation method thereof - Google Patents
Waterborne polyurethane scale-inhibiting coating and preparation method thereof Download PDFInfo
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- CN114702875A CN114702875A CN202210245952.4A CN202210245952A CN114702875A CN 114702875 A CN114702875 A CN 114702875A CN 202210245952 A CN202210245952 A CN 202210245952A CN 114702875 A CN114702875 A CN 114702875A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 135
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 135
- 238000000576 coating method Methods 0.000 title claims abstract description 72
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims description 29
- 230000002401 inhibitory effect Effects 0.000 title claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 102
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 88
- 239000000839 emulsion Substances 0.000 claims abstract description 77
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 73
- 230000005764 inhibitory process Effects 0.000 claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 45
- 238000006116 polymerization reaction Methods 0.000 claims description 53
- 239000003960 organic solvent Substances 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 39
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 34
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 33
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 33
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 33
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 26
- 238000005804 alkylation reaction Methods 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- 150000001340 alkali metals Chemical class 0.000 claims description 17
- 238000006722 reduction reaction Methods 0.000 claims description 17
- -1 1-bromododecyl Chemical group 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 229920001774 Perfluoroether Polymers 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 13
- 238000005299 abrasion Methods 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 68
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 56
- 238000006243 chemical reaction Methods 0.000 description 56
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 44
- 238000001035 drying Methods 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 22
- 238000005406 washing Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 16
- 230000009286 beneficial effect Effects 0.000 description 16
- 238000001914 filtration Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000004945 emulsification Methods 0.000 description 8
- 239000002064 nanoplatelet Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical group [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002152 alkylating effect Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical group OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- QBJDFZSOZNDVDE-UHFFFAOYSA-M sodium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QBJDFZSOZNDVDE-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of high polymer materials. According to the invention, the alkylated graphene is selected, so that the defect that the graphene is easy to agglomerate in a matrix material is overcome, and the perfluoropolyether acrylate modified aqueous polyurethane emulsion with a core-shell structure and excellent thermal stability is selected as the matrix, so that the obtained aqueous polyurethane scale inhibition coating has a better scale inhibition effect and higher water abrasion resistance, stability and hardness under the mutual cooperation effect of the core-shell structure and the matrix. The experimental results show that the high-temperature-resistant steel,the waterborne polyurethane scale inhibition coating provided by the invention has the advantages that the bonding strength can reach (with steel) 15MPa, the Shore D hardness is 70, and the wear resistance is 80mg (1000g, 1000 turns)‑1Water contact angle 101 °; the coating was tested for scale formation in supersaturated calcium carbonate solution at 60 c and the weight of scale formation per square centimeter of test block was only 40mg after 3000 hours immersion of the test block in the solution.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a waterborne polyurethane scale inhibition coating and a preparation method thereof.
Background
The scaling of metal pipelines and pumps is a common problem in the process of pumping and conveying geothermal water, and protective coatings are coated on the surfaces of parts which are easy to scale, such as pipelines, boilers, heat exchangers and the like, so that the method is an effective solution.
The waterborne polyurethane is widely applied as a scale inhibition coating due to the advantages of excellent water resistance, weather resistance, flame resistance, chemical corrosion resistance and the like. However, the water-based polyurethane coating provided by the prior art has a not ideal scale inhibition effect and is limited in water abrasion resistance, stability and hardness, so that the common water-based polyurethane coating is difficult to meet the harsh requirements of the geothermal water high-temperature environment on the coating.
Disclosure of Invention
In view of the above, the invention aims to provide the waterborne polyurethane scale inhibition coating and the preparation method thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a water-based polyurethane scale-inhibiting coating which comprises the following components in parts by weight: 5-50 parts of alkylated graphene and 20-100 parts of perfluoropolyether acrylate modified aqueous polyurethane emulsion.
Preferably, the alkyl group in the alkylated graphene comprises at least one of 1-bromododecyl, octadecyl trichlorosilyl, 1-chlorododecyl and octadecyl tribromosilyl.
Preferably, the preparation method of the alkylated graphene comprises the following steps:
(I) mixing naphthalene, alkali metal, an organic solvent and graphene, and carrying out reduction reaction to obtain reduced graphene;
(II) mixing the reduced graphene obtained in the step (I) with alkane, and carrying out alkylation reaction to obtain alkylated graphene.
Preferably, the weight ratio of the alkali metal to the graphene in the step (I) is (0.10-0.20): (5-40).
Preferably, the weight ratio of the graphene in the step (I) to the alkane in the step (II) is (5-35): 15.
preferably, the preparation method of the perfluoropolyether acrylate modified aqueous polyurethane emulsion comprises the following steps:
(1) mixing methacryloyl chloride, trimeric fluoroether alcohol, an acid-binding agent and an organic solvent, and carrying out a first polymerization reaction to obtain perfluoropolyether acrylate;
(2) mixing isophorone diisocyanate, dimethylolpropionic acid, 1, 4-butanediol, a catalyst and an organic solvent, and carrying out a second polymerization reaction to obtain waterborne polyurethane;
(3) emulsifying the waterborne polyurethane obtained in the step (2) with water to obtain waterborne polyurethane seed emulsion;
(4) mixing the perfluoropolyether acrylate obtained in the step (1) and the aqueous polyurethane emulsion obtained in the step (3) with water, an emulsifier, methyl methacrylate, n-butyl acrylate and an initiator, and carrying out a third polymerization reaction to obtain a perfluoropolyether acrylate modified aqueous polyurethane emulsion;
the steps (1) and (2) are not limited in sequence.
Preferably, the weight ratio of the methacryloyl chloride to the trimeric fluoroether alcohol in the step (1) is (2-8): (40-50).
Preferably, the weight ratio of isophorone diisocyanate, dimethylolpropionic acid and 1, 4-butanediol in the step (2) is (10-17): (1-7): (1-8).
Preferably, the weight ratio of the perfluoropolyether acrylate, the aqueous polyurethane seed emulsion, the methyl methacrylate and the n-butyl acrylate in the step (4) is (10-35): (17-65): (5-60): (5-60).
The invention provides a preparation method of the waterborne polyurethane scale-inhibiting coating in the technical scheme, which comprises the following steps:
and mixing the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion to obtain the mixed aqueous polyurethane scale inhibition coating.
The invention provides a waterborne polyurethane scale-inhibiting coating which comprises the following components in parts by weight: 5-50 parts of alkylated graphene and 20-100 parts of perfluoropolyether acrylate modified aqueous polyurethane emulsion. According to the invention, the alkylated graphene is selected, so that the defect that the graphene is easy to agglomerate in a water-based polyurethane matrix material is greatly improved, the perfluoropolyether acrylate modified water-based polyurethane emulsion with a core-shell structure and excellent thermal stability is selected as a matrix, and under the mutual cooperation effect of the alkylated graphene and the perfluoropolyether acrylate modified water-based polyurethane emulsion, the obtained water-based polyurethane scale inhibition coating has a better scale inhibition effect, and is high in water abrasion resistance, stability and hardness. Experimental results show that the waterborne polyurethane scale inhibition coating provided by the invention has the advantages that the bonding strength can reach (with steel) 15MPa, the Shore D hardness is 70, and the wear resistance is 80mg (1000 g. 1000 turns)-1Water contact angle 101 °; the coating was tested for scale formation in supersaturated calcium carbonate solution at 60 c and the weight of scale formation per square centimeter of test block was only 40mg after 3000 hours immersion of the test block in the solution.
Detailed Description
The invention provides a water-based polyurethane scale-inhibiting coating which comprises the following components in parts by weight: 5-50 parts of alkylated graphene and 20-100 parts of perfluoropolyether acrylate modified aqueous polyurethane emulsion.
The water-based polyurethane scale inhibition coating provided by the invention comprises 5-50 parts by weight of alkylated graphene, preferably 10-30 parts by weight. In the invention, the alkylated graphene has good dispersibility and is not easy to agglomerate in the process of doping the matrix. According to the invention, the dosage of the alkylated graphene is controlled within the range, and the obtained scale inhibition coating has the scale inhibition effect, the water abrasion resistance, the stability and the hardness which can reach ideal values.
In the present invention, the alkyl group in the alkylated graphene preferably includes at least one of 1-bromododecyl group, octadecyltrichlorosilyl group, 1-chlorododecyl group and octadecyltrichlorosilyl group, more preferably 1-bromododecyl group and/or octadecyltrichlorosilyl group, and most preferably 1-bromododecyl group. In the invention, when the alkyl in the alkylated graphene is 1-bromododecyl, the interaction between the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion is optimal, so that the scale inhibition effect, the water abrasion resistance, the stability and the hardness of the obtained aqueous polyurethane scale inhibition coating are better than those of other alkyl.
The aqueous polyurethane scale inhibition coating provided by the invention comprises 20-100 parts of perfluoropolyether acrylate modified aqueous polyurethane emulsion, preferably 35-85 parts by weight of alkylated graphene 5-50 parts by weight. In the invention, the perfluoropolyether acrylate modified aqueous polyurethane emulsion exists as a matrix of the aqueous polyurethane scale-inhibiting coating.
In the present invention, the preparation method of the alkylated graphene preferably comprises the following steps:
(I) mixing naphthalene, alkali metal, an organic solvent and graphene, and carrying out reduction reaction to obtain reduced graphene;
(II) mixing the reduced graphene obtained in the step (I) with alkane, and carrying out alkylation reaction to obtain alkylated graphene.
According to the invention, naphthalene, alkali metal, organic solvent and graphene are preferably mixed for reduction reaction to obtain reduced graphene.
The source of the naphthalene is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. The method is beneficial to promoting the reduction of the alkali metal on the graphene and simultaneously facilitating the alkylation reaction by matching the naphthalene and the alkali metal.
In the present invention, the alkali metal is preferably at least one of lithium, sodium and potassium, and more preferably sodium. The invention takes sodium as a reducing agent, has moderate reaction activity and avoids too slow reaction or too violent reaction.
In the present invention, the organic solvent preferably includes at least one of tetrahydrofuran, dichloromethane, acetone, and xylene, and more preferably tetrahydrofuran. The invention takes tetrahydrofuran as the solvent of the reaction, which is beneficial to fully dissolving naphthalene and alkane, thereby being beneficial to the smooth operation of the reaction.
In the present invention, the graphene is preferably a graphene nanoplatelet. The graphene nanoplatelets are not particularly limited in source, and commercially available products known to those skilled in the art can be used. The invention utilizes the characteristics of excellent mechanical strength, electric conductivity and heat conductivity, and good lubricating, high temperature resistant and corrosion resistant properties of the graphene nanoplatelets to further improve the scale inhibition effect, the water abrasion resistance, the stability and the hardness of the aqueous polyurethane scale inhibition coating.
In the present invention, the weight ratio of naphthalene to alkali metal is preferably (0.05 to 0.15): (0.10 to 0.17), more preferably (0.1 to 0.13): (0.12-0.15). The weight ratio of the naphthalene to the alkali metal is controlled in the range, so that the reduction of the graphene by the alkali metal can be fully promoted, and the alkylation reaction can be fully promoted, thereby further improving the scale inhibition effect, the water abrasion resistance, the stability and the hardness of the aqueous polyurethane scale inhibition coating.
In the invention, the weight ratio of the alkali metal to the graphene is preferably (0.10-0.20): (5-40), more preferably (0.12-0.15): (10-30). According to the invention, the weight ratio of the alkali metal to the graphene is controlled within the range, so that the graphene can be fully reduced, and the scale inhibition effect, the water abrasion resistance, the stability and the hardness of the aqueous polyurethane scale inhibition coating are further improved.
In the invention, the weight ratio of the organic solvent to the graphene is preferably (30-60): (5-40), more preferably 50: (10-30). The invention controls the dosage of the organic solvent in the range, and the organic solvent plays a role in fully dissolving the reaction raw materials, so that the raw materials are uniformly dispersed, and the full reaction is promoted.
According to the invention, preferably, naphthalene and alkali metal are added into an organic solvent, then graphene is added, reduction reaction is carried out, and then ultrasound is carried out to obtain the reduced graphene. The method for feeding the graphene is favorable for uniformly dispersing all the raw materials in the organic solvent, so that the graphene can be fully reduced.
In the present invention, the temperature of the reduction reaction is preferably room temperature. The invention utilizes the characteristic that alkali metal has strong reducibility at room temperature, thereby utilizing the room temperature condition to carry out reduction reaction.
In the present invention, the reduction reaction is preferably carried out under stirring conditions. In the invention, the stirring speed in the reduction reaction is preferably 50-200 r/min, and more preferably 100-180 r/min. The invention adopts the stirring speed to carry out the reduction reaction, which is beneficial to the full implementation of the reduction reaction.
In the present invention, the time of the reduction reaction is preferably 20 to 30 hours, and more preferably 24 hours. The invention adopts the reaction time, which is beneficial to the full implementation of the reduction reaction.
The ultrasonic mode is not specially specified, and the reaction device is put into water for ultrasonic treatment by adopting the ultrasonic mode which is well known to a person skilled in the art. In the invention, the time of the ultrasonic treatment is preferably 0.5 to 2 hours, and more preferably 1 hour. The invention adopts the time for ultrasonic treatment, which is beneficial to uniformly dispersing all substances in a reaction system after alkylation reaction and is beneficial to further reaction of substances which are not reacted in a reduction reaction stage.
After the reduced graphene is obtained, the reduced graphene and alkane are preferably mixed for alkylation reaction to obtain the alkylated graphene.
In the invention, the weight ratio of the graphene to the alkane is preferably (5-35): 15, more preferably (10 to 30): 15. according to the invention, the weight ratio of the graphene to the alkane is controlled within the range, so that the alkylation modification of the obtained reduced graphene can be fully realized, the dispersity of the alkylated graphene is improved, and the alkylated graphene is not easy to agglomerate in the process of doping a matrix, and the scale inhibition effect, the water abrasion resistance, the stability and the hardness of the aqueous polyurethane scale inhibition coating are further improved.
In the present invention, the order of mixing the reduced graphene and the alkane is preferably that the alkane is added to the reduced graphene.
In the present invention, the alkane is preferably added dropwise.
The dropping mode is not specially specified in the invention, and the feeding can be carried out by adopting the dropping mode which is well known to the technical personnel in the field. The method adopts a dropwise adding mode to feed materials, avoids the reaction from being too violent, and is beneficial to fully carrying out the alkylation reaction.
The present invention preferably terminates the alkylation reaction by adding a terminator to the system of the alkylation reaction. In the present invention, the terminator is preferably cyclohexane and water. In the present invention, the order of addition of cyclohexane and water is preferably that cyclohexane is added first and then water is added. According to the method, the alkylation reaction is quenched by adding the organic cyclohexane first and then adding the water, so that the phenomenon that the quenching effect of the cyclohexane serving as the organic is reduced due to poor compatibility of the water and an organic reaction system is avoided.
In the invention, the weight ratio of cyclohexane to graphene in the terminator is preferably (5-30): (5-35), more preferably (10-20): (10-30). In the invention, the weight ratio of water to graphene in the terminator is preferably (50-100): (5-35), more preferably (60-80): (10-30). The present invention controls the amount of cyclohexane and water within the above range, and can completely stop the alkylation reaction, and the excessive water can dispose the excessive alkali metal.
After the alkylation reaction is completed, the alkylation reaction product is preferably washed, filtered, washed with an organic solvent and dried in sequence to obtain the alkylated graphene.
The water washing mode is not specially specified in the invention, and substances dissolved in water can be removed by utilizing a water washing mode well known to a person skilled in the art.
The filtration method is not particularly specified in the present invention, and the alkylated graphene may be filtered out of the solution by a filtration method well known to those skilled in the art. In the present embodiment, membrane filtration is preferably employed.
In the present invention, the drying method is preferably vacuum drying. According to the invention, a vacuum drying mode is adopted to avoid the influence of oxygen in the air on the alkylated graphene.
In the present invention, the temperature for the drying is preferably 50 to 70 ℃, more preferably 60 ℃. In the invention, the drying time is preferably 20-48 h, and more preferably 248 h. The invention limits the drying temperature to the range, can realize the full drying of the alkylated graphene, and does not influence the performance of the alkylated graphene.
The alkylated graphene prepared by the technical scheme has good dispersibility.
In the present invention, the preparation method of the perfluoropolyether acrylate modified aqueous polyurethane emulsion preferably comprises the following steps:
(1) mixing methacryloyl chloride, trimeric fluoroether alcohol, an acid-binding agent and an organic solvent, and carrying out a first polymerization reaction to obtain perfluoropolyether acrylate;
(2) mixing isophorone diisocyanate, dimethylolpropionic acid, 1, 4-butanediol, a catalyst and an organic solvent, and carrying out a second polymerization reaction to obtain waterborne polyurethane;
(3) emulsifying the waterborne polyurethane obtained in the step (2) with water to obtain waterborne polyurethane seed emulsion;
(4) mixing the perfluoropolyether acrylate obtained in the step (1) and the aqueous polyurethane seed emulsion obtained in the step (3) with an emulsifier, methyl methacrylate, n-butyl acrylate and an initiator, and carrying out a third polymerization reaction to obtain a perfluoropolyether acrylate modified aqueous polyurethane emulsion;
the steps (1) and (2) are not limited in sequence.
In the present invention, the entire process for preparing the perfluoropolyether acrylate is preferably carried out in a reactor. The present invention preferably dries the reactor and all reaction mass prior to preparation. According to the invention, the reactor and the reaction materials are dried in advance, so that the influence of moisture on the first polymerization reaction is avoided, and the smooth proceeding of the first polymerization reaction is ensured.
According to the invention, preferably, methacryloyl chloride, the trimeric fluoroether alcohol, the acid-binding agent and the organic solvent are mixed for carrying out a first polymerization reaction to obtain the perfluoropolyether acrylate.
The source of the methacryloyl chloride and the fluoroether alcohol is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
The acid-binding agent is not particularly limited in kind, and acid in the reaction process is neutralized by the acid-binding agent well known to those skilled in the art to promote the first polymerization reaction, and triethylamine is preferred in the embodiment of the present invention.
In the present invention, the organic solvent preferably includes at least one of dichloromethane, acetone, and xylene, and more preferably dichloromethane. In the invention, the dichloromethane can not only fully dissolve the raw materials to promote the reaction, but also has low energy consumption for solvent post-treatment due to the low boiling point of the dichloromethane.
In the invention, the weight ratio of the methacryloyl chloride to the trimeric fluoroether alcohol is preferably (2-8): (40-50), more preferably (4-6): (30-35). In the present invention, the amounts of the methacryloyl chloride and the trifluoroetherol to be used are controlled within the above ranges, and the first polymerization reaction can be sufficiently performed.
In the invention, the weight ratio of the acid-binding agent to the trimeric fluoroether alcohol is preferably (2-8): (40-50), more preferably (20-50): (20-40), more preferably (30-40): (30-35). In the present invention, the amount of the acid scavenger is controlled within the above range, and the acid generated in the first polymerization reaction can be completely neutralized to promote the smooth progress of the first polymerization reaction.
In the invention, the weight ratio of the organic solvent to the trimeric fluoroether alcohol is preferably (5-20): (40-50), more preferably (8-12): (30-35). The invention controls the dosage of the organic solvent in the range, can realize the complete dissolution of materials and ensure the smooth operation of the first polymerization reaction.
In the present invention, the mixture of the methacryloyl chloride, the polyfluoroether alcohol, the acid-binding agent and the organic solvent is preferably: methacrylic chloride, an acid-binding agent and an organic solvent are mixed, and then the polyfluoroether alcohol is added.
In the present invention, the condition for adding the polyfluoroether alcohol is preferably ice water bath. In the present invention, the addition manner of the trimeric fluoroether alcohol is preferably slow. In the invention, the total time for adding the trimeric fluoroether alcohol is preferably 20-50 min, and more preferably 30 min. The invention adopts a mode of slowly adding the polyfluoroether alcohol in an ice-water bath, avoids the excessively violent reaction of the methacryloyl chloride and the polyfluoroether alcohol, and simultaneously avoids the implosion.
In the present invention, the temperature of the first polymerization reaction is preferably room temperature. In the present invention, the time of the first polymerization reaction is preferably 5 to 20 hours, and more preferably 10 hours. The invention adopts the reaction temperature and the reaction time, which is beneficial to the full implementation of the first polymerization reaction.
After the first polymerization reaction is completed, the present invention preferably performs a post-treatment on the product of the first polymerization reaction to obtain perfluoropolyether acrylate.
In the present invention, the post-treatment preferably comprises water washing, drying, filtration, rotary evaporation and chromatography, which are sequentially performed.
The method of washing with water in the present invention is not particularly limited, and substances dissolved in water may be removed by a washing method known to those skilled in the art. The invention removes the impurities dissolved in water mixed in the organic phase by a water washing mode.
In the present invention, the dried reagent is preferably anhydrous magnesium sulfate and/or anhydrous sodium sulfate, and more preferably anhydrous magnesium sulfate. The invention selects anhydrous magnesium sulfate with larger water absorption capacity to fully remove the water in the organic phase.
The filtration method is not particularly specified in the present invention, and the solids in the liquid can be removed by filtration methods well known to those skilled in the art. The invention adopts a filtration mode to remove the drying agent in the organic phase.
The rotary evaporation mode is not specially specified in the invention, and the solvent can be removed by adopting a rotary evaporation mode well known to those skilled in the art. The invention adopts a rotary evaporation mode to remove the organic solvent dissolved with the product.
The mode of chromatography is not particularly specified in the present invention, and the product can be separated from impurities by a chromatography method well known to those skilled in the art. In the embodiment of the invention, the separation of the product and the impurities is preferably realized by adopting a column chromatography mode.
According to the invention, isophorone diisocyanate, dimethylolpropionic acid, 1, 4-butanediol, a catalyst and an organic solvent are preferably mixed to carry out a second polymerization reaction, so that the waterborne polyurethane is obtained.
In the present invention, the catalyst in the second polymerization reaction preferably includes at least one of dibutyltin dilaurate, potassium persulfate, and sodium persulfate, and more preferably dibutyltin dilaurate. According to the invention, dibutyltin dilaurate which has excellent solubility in an organic solvent and stable properties is selected as a catalyst for the second polymerization reaction, so that the second polymerization reaction is promoted to be fully carried out.
In the present invention, the organic solvent preferably includes at least one of tetrahydrofuran, dichloromethane, acetone, and xylene, and more preferably tetrahydrofuran. The invention takes tetrahydrofuran as the solvent of the reaction, which is beneficial to the full dissolution of the reaction materials, thereby being beneficial to the smooth operation of the reaction.
In the invention, the weight ratio of the isophorone diisocyanate to the dimethylolpropionic acid to the 1, 4-butanediol is preferably (10-17): (1-7): (1-8), more preferably (12-15): (2-5): (3-5). According to the invention, the dosage of the isophorone diisocyanate, the dimethylolpropionic acid and the 1, 4-butanediol is controlled in the above range, so that the second polymerization reaction can be fully performed.
In the invention, the weight ratio of the isophorone diisocyanate to the catalyst is preferably (10-17): (1-7), more preferably (12-15): (3-5). According to the invention, the dosage of the isophorone diisocyanate and the catalyst is controlled within the above range, so that the second polymerization reaction can be fully performed.
In the invention, the weight ratio of the isophorone diisocyanate to the organic solvent is preferably (10-17): (20-60), more preferably (12-15): (30-50). The invention controls the dosage of the organic solvent in the range, is favorable for fully dissolving the materials and promoting the full progress of the second polymerization reaction.
In the present invention, the organic solvent is preferably dried before use. In the invention, the drying temperature is preferably 80-110 ℃, and more preferably 90-100 ℃; the drying pressure is preferably 0.08-0.10 MPa, and more preferably 0.09 MPa; the drying time is preferably 5-9 h, and more preferably 6-8 h. The organic solvent is dried before use, so that the influence of moisture in the solvent on the second polymerization reaction is avoided, and the smooth operation of the second polymerization reaction is facilitated.
According to the invention, the organic solvent and isophorone diisocyanate are preferably mixed first, and then dimethylolpropionic acid, 1, 4-butanediol and dibutyltin dilaurate are sequentially added. According to the invention, the organic solvent and the isophorone diisocyanate are mixed, so that the viscosity of the isophorone diisocyanate in a reaction system is favorably reduced; as the dimethylolpropionic acid is solid, the dimethylolpropionic acid is added before the liquid 1, 4-butanediol so as to be beneficial to the full reaction between the dimethylolpropionic acid and the 1, 4-butanediol, and finally, a catalyst is added to catalyze the reaction.
In the present invention, the mixing manner of the organic solvent and isophorone diisocyanate is preferably to add isophorone diisocyanate dropwise to the organic solvent. The dropping mode is not specially specified in the invention, and the isophorone diisocyanate is dropwise added into the organic solvent by using the dropping mode which is well known to those skilled in the art. According to the invention, the organic solvent and the isophorone diisocyanate are mixed in a dropwise manner, so that the phenomenon that materials are splashed due to the mixing of the materials at high temperature is avoided.
In the present invention, the mixing of the organic solvent and isophorone diisocyanate is preferably performed under stirring conditions. In the invention, the stirring speed in the mixing of the organic solvent and the isophorone diisocyanate is preferably 100-200 r/min, and more preferably 100 r/min. In the invention, the mixing temperature of the organic solvent and isophorone diisocyanate is preferably 60-80 ℃, and more preferably 75 ℃. In the invention, the mixing time of the organic solvent and isophorone diisocyanate is preferably 0.5-2 h, and more preferably 1.5 h. The adoption of the stirring speed, the mixing temperature and the mixing time is beneficial to fully dissolving the isophorone diisocyanate in the organic solvent.
In the invention, preferably, before adding the dimethylolpropionic acid, the 1, 4-butanediol and the dibutyltin dilaurate, the mixture of the organic solvent and the isophorone diisocyanate is subjected to heat preservation treatment at a second polymerization temperature.
In the invention, the time of the heat preservation treatment is preferably 1-2 h, and more preferably 1.5 h. The mixture of the organic solvent and the isophorone diisocyanate is subjected to heat preservation treatment by adopting the time, so that the viscosity of a reaction system is further reduced, and the second polymerization reaction is further facilitated.
In the present invention, the dimethylolpropionic acid is preferably added in the form of a dimethylolpropionic acid solution. In the present invention, the solvent in the dimethylolpropionic acid solution is preferably N-methylpyrrolidone. According to the invention, the mode that N-methyl pyrrolidone dissolves dimethylolpropionic acid is adopted, solid dimethylolpropionic acid is converted into liquid for adding materials, so that on one hand, the solvent splashing caused when solid materials are added into a high-temperature solvent is avoided, on the other hand, the raw materials can react in a liquid-liquid manner, and the reaction is promoted to be fully carried out.
In the invention, the weight ratio of the dimethylolpropionic acid to the N-methylpyrrolidone is preferably (1-7): (10-30), more preferably (2-5): (20-25). According to the invention, the dosage of the dimethylolpropionic acid and the N-methyl pyrrolidone are controlled within the above range, the dimethylolpropionic acid can be fully dissolved in the N-methyl pyrrolidone, the concentration of the dimethylolpropionic acid when the dimethylolpropionic acid is added into a reaction system is reduced, and the reaction is prevented from being too violent.
In the present invention, the temperature of the second polymerization reaction is preferably 75 to 90 ℃, and more preferably 80 ℃. The time of the second polymerization reaction is preferably 2 to 5 hours, and more preferably 3 to 4 hours. The temperature and time of the second polymerization reaction are controlled within the above ranges, which is favorable for the full reaction.
After the second polymerization reaction is finished, the invention preferably carries out end capping and neutralization on the products of the polymerization reaction in sequence to obtain the waterborne polyurethane.
In the present invention, the agent used for the end-capping is preferably 2-hydroxyethyl methacrylate. The invention takes methacrylic acid-2-hydroxyethyl ester as an end-capping reagent to eliminate the activity of the end group functional group of the second polymerization reaction and terminate the polymerization reaction.
In the end capping process, the present invention preferably adds a diluent to the reaction system. The invention reduces the viscosity of the reaction system by adding the diluent.
In the present invention, the diluent is preferably acetone and/or tetrahydrofuran, more preferably acetone. The invention selects acetone with relatively lower viscosity as the diluent, which is more favorable for reducing the viscosity of the reaction system.
The weight ratio of the diluent to isophorone diisocyanate used for preparing waterborne polyurethane in the invention is preferably (40-70): (7-23), more preferably (50-60): (12-15). The present invention controls the viscosity of the reaction system in an appropriate range by controlling the amount of the diluent in the above range.
In the invention, the temperature of the end capping is preferably 60-70 ℃, and more preferably 65 ℃. In the invention, the end-capping time is preferably 3-6 h, and more preferably 4-5 h. The present invention can sufficiently inactivate the terminal functional group of the second polymerization reaction by controlling the temperature and time of the end-capping within the above-mentioned ranges.
The reagent used in the neutralization is not particularly limited in the present invention, and the acid produced in the second polymerization reaction can be sufficiently neutralized by an alkaline substance known to those skilled in the art. In the present invention, the neutralizing agent is preferably triethylamine.
In the invention, the weight ratio of the reagent used in neutralization and isophorone diisocyanate used for preparing the waterborne polyurethane is preferably (20-50): (7-23), more preferably (30-45): (12-15). In the invention, the neutralization time is preferably 0.2-1 h, and more preferably 0.5 h. The present invention can ensure sufficient neutralization of the acid produced in the reaction system by controlling the amount of the reagent used in the neutralization and the time for the neutralization within the above-mentioned ranges.
In the invention, the neutralization temperature is preferably 30-50 ℃, and more preferably 40 ℃. In the present invention, the temperature for neutralization is controlled within the above range, and the acid generated in the reaction system can be sufficiently neutralized.
After obtaining the waterborne polyurethane, the waterborne polyurethane and water are preferably mixed and emulsified to obtain the waterborne polyurethane seed emulsion.
The emulsifying mode is not specially specified in the invention, and the waterborne polyurethane and the water can be fully emulsified by adopting the emulsifying mode which is well known to the technical personnel in the field.
In the present invention, the weight ratio of the water to the isophorone diisocyanate used for preparing the aqueous polyurethane is preferably 70: (7-23), more preferably 70: (12-15). According to the invention, the water-based polyurethane and water can be fully emulsified by controlling the using amount of the water within the range.
After the perfluoropolyether acrylate and the aqueous polyurethane seed emulsion are obtained, the perfluoropolyether acrylate and the aqueous polyurethane seed emulsion are preferably mixed with water, an emulsifier, methyl methacrylate, n-butyl acrylate and an initiator to carry out a third polymerization reaction, so that the perfluoropolyether acrylate modified aqueous polyurethane emulsion is obtained.
In the present invention, the emulsifier is preferably potassium perfluorobutylsulfonate and/or sodium perfluorobutylsulfonate. The invention selects the emulsifier containing the perfluorobutyl sulfonic acid group, which is beneficial to increasing the compatibility between the emulsifier and the perfluoropolyether acrylate and ensures that the emulsification is better and more sufficient.
In the present invention, the initiator includes potassium persulfate and/or sodium persulfate. The initiator is selected, so that the third polymerization reaction can be promoted to be fully carried out.
In the invention, the weight ratio of the perfluoropolyether acrylate to the aqueous polyurethane seed emulsion to the methyl methacrylate to the n-butyl acrylate is preferably (10-35): (17-65): (5-60): (5-60), more preferably (20-25): (25-55): (10-50): (10-50). The method controls the dosage of the perfluoropolyether acrylate, the waterborne polyurethane seed emulsion, the methyl methacrylate and the n-butyl acrylate in the above range, and the obtained perfluoropolyether acrylate modified waterborne polyurethane emulsion has the best performance.
In the invention, the weight ratio of the aqueous polyurethane seed emulsion, water and the emulsifier is preferably (17-65): (20-25): (5-60), preferably (10-35): (22-24): (20-25). According to the invention, the water-based polyurethane seed emulsion, the water and the emulsifier are controlled within the above range, so that the water-based polyurethane emulsion can be emulsified more fully.
In the invention, the weight ratio of the initiator to the perfluoropolyether acrylate is preferably (3-20): (10-35), preferably (5-15): (20-25). The present invention can promote the third polymerization reaction to proceed sufficiently by controlling the amount of the initiator to the above range.
Preferably, the method comprises the steps of mixing the waterborne polyurethane seed emulsion, water and the emulsifier, adding the perfluoropolyether acrylate, the methyl methacrylate and the n-butyl acrylate, pre-emulsifying, standing, adding the initiator, performing a third polymerization reaction, and cooling to obtain the perfluoropolyether acrylate modified waterborne polyurethane emulsion. In the present invention, the perfluoropolyether acrylate, methyl methacrylate, and n-butyl acrylate are all pre-emulsified acrylate monomers. According to the invention, the mode of mixing the waterborne polyurethane seed emulsion, water and the emulsifier is adopted, so that the acrylate monomer added later can be fully pre-emulsified in a reaction system.
The mixing mode of the aqueous polyurethane emulsion, the water and the emulsifier is not specially specified, and the aqueous polyurethane emulsion, the water and the emulsifier are uniformly mixed by adopting a mixing mode well known by the technical personnel in the field.
In the present invention, the mixing of the aqueous polyurethane emulsion, water and the emulsifier is preferably performed under stirring conditions; the stirring temperature is preferably room temperature; the stirring speed is preferably 50-200 r/min, and more preferably 100-180 r/min; the stirring time is preferably 5-20 min, and more preferably 10 min. The invention can realize the full mixing of the aqueous polyurethane emulsion water and the emulsifier by adopting the stirring speed and the stirring time, and is favorable for full pre-emulsification of the acrylate monomer in a reaction system.
In the invention, the pre-emulsification temperature is preferably 40-50 ℃, and more preferably 45 ℃. In the invention, the stirring speed required in the pre-emulsification is preferably 300-400 r/min, and more preferably 350 r/min; the pre-emulsification time is preferably 0.5-2 h, and more preferably 1 h. The invention can realize the full emulsification among the acrylate monomers by adopting the pre-emulsification temperature, time and the stirring speed required during the pre-emulsification.
In the invention, the standing time is preferably 0.5-2 h, and more preferably 1-1.5 h. The invention adopts the standing time to realize the full swelling of the acrylate monomer.
In the present invention, it is preferable that the initiator and the solvent are mixed and then slowly added to the reaction system. In the present invention, when the initiator is potassium persulfate, the corresponding solvent is preferably water. The amount of the solvent used in the present invention is not particularly limited, and the initiator may be dissolved in an amount well known to those skilled in the art.
In the invention, the total time of the slow addition is preferably 1-3 h, and more preferably 2 h. The initiator is slowly added, and the adding time is controlled within the range so as to avoid implosion.
In the present invention, the third polymerization reaction is preferably in N2Under protection. The invention adopts N2And the protection is carried out, so that the influence of oxygen in the air on the third polymerization reaction in the reaction process is avoided, and the smooth operation of the third polymerization reaction is facilitated.
In the present invention, the third polymerization reaction is preferably carried out under stirring conditions. In the invention, the stirring speed in the third polymerization reaction is preferably 100-300 r/min, and more preferably 150-200 r/min; the stirring time is preferably 1-4 h, and more preferably 3 h. The invention is accompanied by stirring in the process of the third polymerization reaction, and is beneficial to the formation of emulsion by the product generated by the third polymerization reaction.
In the present invention, the cooling mode is preferably natural cooling.
In the invention, the final temperature of the temperature reduction is preferably 30-45 ℃, and more preferably 40 ℃. The invention reduces the temperature of the reaction system to the temperature, which is beneficial to pouring the materials out of the reactor.
The invention also provides a preparation method of the waterborne polyurethane scale inhibition coating in the technical scheme, which comprises the following steps:
and mixing the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion to obtain the mixed aqueous polyurethane scale inhibition coating.
According to the invention, preferably, the alkylated graphene is added into the perfluoropolyether acrylate modified aqueous polyurethane emulsion and mixed to obtain the mixed aqueous polyurethane scale inhibition coating.
In the invention, the time for adding the alkylated graphene is preferably 0.5-1.5 h, and more preferably 0.8-1 h. According to the invention, the time for adding the alkylated graphene is controlled within the range, so that the alkylated graphene and the perfluoropolyether acrylate modified waterborne polyurethane emulsion can be fully mixed.
In the invention, the mixing of the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion is preferably carried out under the stirring condition; the stirring speed is preferably 100-250 r/min, and more preferably 200 r/min; the stirring time is preferably 0.5-1.5 h, and more preferably 1 h. According to the invention, the fully mixing of the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion can be realized by adopting the stirring speed and the stirring time.
In the invention, the mixing temperature of the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion is preferably 70-100 ℃, and more preferably 80-90 ℃. The fully mixing of the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion can be realized by adopting the mixing temperature.
After the mixing of the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion is finished, the mixed product is preferably subjected to vacuum pumping and pressurization in sequence to obtain the aqueous polyurethane scale inhibition coating.
The invention has no special regulation on the vacuumizing mode, and the vacuumizing mode known to a person skilled in the art is adopted to reduce the pressure of the system so as to be convenient for removing the solvent in the reaction system.
The pressurizing mode is not specially specified in the invention, and the solvent in the reaction system can be conveniently removed by adopting the pressurizing mode which is well known to a person skilled in the art. Nitrogen pressurization is preferred in the present embodiment.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of alkylated graphene
Dispersing 0.1 parts by weight of naphthalene and 0.12 parts by weight of sodium in 50 parts by weight of tetrahydrofuran, and then dispersing 10 parts by weight of graphene nanoplatelets; stirring for 24 hours at room temperature at the stirring speed of 100r/min, then carrying out ultrasonic treatment for 1 hour, then dropwise adding 15 parts by weight of alkylating reagent 1-bromododecane into the reaction system, and continuously stirring for 24 hours; and finally, respectively adding 10 parts by weight of cyclohexane and 70 parts by weight of deionized water to terminate the alkylation reaction, washing with the deionized water, then filtering with a polytetrafluoroethylene membrane (0.22 mu m), washing a filter cake with the cyclohexane, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the alkylated graphene.
Preparation of perfluoropolyether acrylate modified waterborne polyurethane emulsion
(1) Adding methacryloyl chloride and CH into a three-neck flask2Cl2Triethylamine and polyfluoroether alcohol (added after 30 minutes) are added under the condition of ice-water bath, and the reaction is carried out for 10 hours at room temperature; washing the organic phase with distilled water after the reaction is finished, drying with anhydrous magnesium sulfate, filtering, removing the solvent by rotation, and purifying by column chromatography to obtain colorless oily liquid perfluoropolyether acrylate (methacryloyl chloride, CH)2Cl2The weight ratio of triethylamine to the trifluoroether alcohol is 3: 10: 30: 30, of a nitrogen-containing gas; the three-mouth bottle and methacryloyl chloride and CH2Cl2Triethylamine and the trifluoroetherol are subjected to drying treatment).
(2) In a reflux condenser pipe, a mechanical stirrer, a thermometer and N2Adding 3 parts by weight of tetrahydrofuran into a protected four-neck flask, heating to 75 ℃ under stirring at 100r/min, dropwise adding 12 parts by weight of isophorone diisocyanate, heating to 80 ℃, keeping the temperature for 1.5h, adding 2 parts by weight of dimethylolpropionic acid, dissolving the dimethylolpropionic acid in 20 parts of N-methylpyrrolidone, adding 3 parts by weight of 1, 4-butanediol and dibutyltin dilaurate, keeping the temperature for 3h at 80 ℃, reducing the temperature to 65 ℃, adding 10 parts by weight of 2-hydroxyethyl methacrylate for blocking, and adding 50 parts by weight of acetone during the process to reduce the viscosity of the system. And after 4h, cooling the temperature to 40 ℃, adding 30 parts by weight of triethylamine to neutralize for 0.5h, and adding 70 parts by weight of deionized water at room temperature to emulsify for 1h to obtain the semitransparent bluish waterborne polyurethane seed emulsion. (the tetrahydrofuran was dried under the conditions of 90 ℃ and 0 ℃.And drying for 6h under the condition of 09 MPa).
(3) Is equipped with reflux condenser tube, mechanical stirrer, thermometer and N218 parts by weight of waterborne polyurethane seed emulsion, deionized water and 25 parts by weight of emulsifier (potassium perfluorobutylsulfonate) are added into a protected four-mouth bottle, and stirred at room temperature for 10min at 100 r/min. Heating to 45 ℃, dropwise adding 25 parts by weight of perfluoropolyether acrylate, 10 parts by weight of methyl methacrylate and 10 parts by weight of n-butyl acrylate, stirring for 1h at 350r/min to fully pre-emulsify the acrylate monomer, and standing for 1h to fully swell the acrylate monomer. Heating to 75 ℃, adding 10 parts by weight of potassium persulfate at the speed of 200r/min, dissolving the potassium persulfate with water, adding the potassium persulfate within 2 hours, keeping the temperature for 3 hours, cooling to 40 ℃, and discharging to obtain the perfluoropolyether acrylate modified waterborne polyurethane emulsion.
Preparation of water-based polyurethane scale-inhibiting coating
Adding 35 parts by weight of the synthesized perfluoropolyether acrylate modified waterborne polyurethane emulsion into a dispersion pot, heating to 70 ℃, starting stirring, stirring for 1h at the speed of 150r/min, slowly adding 10 parts by weight of alkylated graphene under the stirring condition, adding the alkylated graphene for 0.8h, stirring for 1h, vacuumizing for 1h, and pressurizing with nitrogen for 30min to obtain the waterborne polyurethane scale inhibition coating.
Example 2
Preparation of alkylated graphene
Dispersing 0.13 parts by weight of naphthalene and 0.15 parts by weight of sodium in 50 parts by weight of tetrahydrofuran, and then dispersing 30 parts by weight of graphene nanoplatelets; stirring for 24 hours at room temperature at the stirring speed of 150r/min, then carrying out ultrasonic treatment for 1 hour, then dropwise adding 15 parts by weight of alkylating agent 1-bromododecane into the reaction system, and continuously stirring for 24 hours; and finally, respectively adding 10 parts by weight of cyclohexane and 70 parts by weight of deionized water to terminate the alkylation reaction, washing with the deionized water, then filtering with a polytetrafluoroethylene membrane (0.22 mu m), washing a filter cake with the cyclohexane, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the alkylated graphene.
Preparation of perfluoropolyether acrylate modified waterborne polyurethane emulsion
Adding methacryloyl to a three-necked bottleChlorine, CH2Cl2Triethylamine and polyfluoroether alcohol (added after 30 minutes) are added under the condition of ice-water bath, and the reaction is carried out for 10 hours at room temperature; washing the organic phase with distilled water after the reaction is finished, drying with anhydrous magnesium sulfate, filtering, removing the solvent by rotation, and purifying by column chromatography to obtain colorless oily liquid perfluoropolyether acrylate (methacryloyl chloride, CH)2Cl2The weight ratio of triethylamine to the trimeric fluoroether alcohol is 4: 10: 35: 32, a first step of removing the first layer; the three-mouth bottle and methacryloyl chloride and CH2Cl2Triethylamine and the trifluoroetherol are subjected to drying treatment).
In a reflux condenser pipe, a mechanical stirrer, a thermometer and N2Adding 4 parts by weight of tetrahydrofuran into a protected four-neck flask, heating to 75 ℃ under the stirring of 100r/min, dropwise adding 13 parts by weight of isophorone diisocyanate, heating to 82 ℃, keeping the temperature for 1.5h, adding 3 parts by weight of dimethylolpropionic acid, dissolving the dimethylolpropionic acid in 22 parts of N-methyl pyrrolidone, adding 4 parts by weight of 1, 4-butanediol and dibutyltin dilaurate, keeping the temperature for 3h at 82 ℃, reducing the temperature to 65 ℃, adding 15 parts by weight of 2-hydroxyethyl methacrylate for blocking, and adding 50 parts by weight of acetone during the process to reduce the viscosity of the system. And after 4h, cooling the temperature to 40 ℃, adding 35 parts by weight of triethylamine to neutralize for 0.5h, and adding 70 parts by weight of deionized water at room temperature to emulsify for 1h to obtain the semitransparent bluish waterborne polyurethane seed emulsion. (the tetrahydrofuran is dried under the condition of vacuum drying for 6h at 90 ℃ and 0.09 MPa).
In a reflux condenser pipe, a mechanical stirrer, a thermometer and N226 parts by weight of waterborne polyurethane seed emulsion, deionized water and 25 parts by weight of emulsifier (potassium perfluorobutylsulfonate) are added into a protected four-mouth bottle, and stirred at room temperature for 10min at 100 r/min. Heating to 45 ℃, dropwise adding 25 parts by weight of perfluoropolyether acrylate, 10 parts by weight of methyl methacrylate and 10 parts by weight of n-butyl acrylate, stirring for 1h at 350r/min to fully pre-emulsify the acrylate monomer, and standing for 1h to fully swell the acrylate monomer. Heating to 75 ℃, adding 10 parts by weight of potassium persulfate at the speed of 200r/min, dissolving the potassium persulfate with water, adding the potassium persulfate within 2 hours, and preserving heatAnd (3) cooling to 40 ℃ and discharging to obtain the perfluoropolyether acrylate modified waterborne polyurethane emulsion.
Preparation of water-based polyurethane scale-inhibiting coating
Adding 47 parts by weight of the synthesized perfluoropolyether acrylate modified waterborne polyurethane emulsion into a dispersion pot, heating to 80 ℃, starting stirring, stirring for 1h at the speed of 150r/min, slowly adding 20 parts by weight of alkylated graphene under the stirring condition, adding the alkylated graphene for 0.8h, stirring for 1h, vacuumizing for 1h, and pressurizing for 30min with nitrogen to obtain the waterborne polyurethane scale inhibition coating.
Example 3:
preparation of alkylated graphene
Dispersing 0.13 parts by weight of naphthalene and 0.15 parts by weight of sodium in 50 parts by weight of tetrahydrofuran, and then dispersing 30 parts by weight of graphene nanoplatelets; stirring for 24 hours at room temperature at the stirring speed of 100r/min, then carrying out ultrasonic treatment for 1 hour, then dropwise adding 15 parts by weight of alkylating reagent 1-bromododecane into the reaction system, and continuously stirring for 24 hours; and finally, respectively adding 10 parts by weight of cyclohexane and 70 parts by weight of deionized water to terminate the alkylation reaction, washing with the deionized water, then filtering with a polytetrafluoroethylene membrane (0.22 mu m), washing a filter cake with the cyclohexane, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the alkylated graphene.
Preparation of perfluoropolyether acrylate modified waterborne polyurethane emulsion
Adding methacryloyl chloride and CH into a three-mouth bottle2Cl2Triethylamine and polyfluoroether alcohol (added after 30 minutes) are added under the condition of ice-water bath, and the reaction is carried out for 10 hours at room temperature; washing the organic phase with distilled water after the reaction is finished, drying with anhydrous magnesium sulfate, filtering, removing the solvent by rotation, and purifying by column chromatography to obtain colorless oily liquid perfluoropolyether acrylate (methacryloyl chloride, CH)2Cl2The weight ratio of triethylamine to the trimeric fluoroether alcohol is 5: 10: 40: 35; the three-mouth bottle and methacryloyl chloride and CH2Cl2Triethylamine and the trifluoroetherol are subjected to drying treatment).
In a reflux condenser pipe, a mechanical stirrer, a thermometer and N2Adding 5 into a protected four-neck flaskHeating tetrahydrofuran in weight portion to 75 deg.c under stirring at 100r/min, dropping isophorone diisocyanate in 15 weight portions, heating to 82 deg.c, maintaining for 1.5 hr, adding dimethylolpropionic acid in 4 weight portions and dissolving dimethylolpropionic acid in 25 weight portions, adding 1, 4-butanediol and dibutyltin dilaurate in 5 weight portions, maintaining at 82 deg.c for 3 hr, lowering the temperature to 65 deg.c, adding 2-hydroxyethyl methacrylate in 20 weight portions to terminate, and adding acetone in 55 weight portions to lower the viscosity of the system. And after 4h, cooling the temperature to 40 ℃, adding 40 parts by weight of triethylamine to neutralize for 0.5h, and adding 70 parts by weight of deionized water at room temperature to emulsify for 1h to obtain the semitransparent bluish waterborne polyurethane seed emulsion. (the tetrahydrofuran is dried under the condition of vacuum drying for 6h at 90 ℃ and 0.09 MPa).
In a reflux condenser pipe, a mechanical stirrer, a thermometer and N237 parts by weight of waterborne polyurethane seed emulsion, deionized water and 25 parts by weight of emulsifier (potassium perfluorobutylsulfonate) are added into a protected four-mouth bottle, and stirred at room temperature for 10min at 100 r/min. Heating to 45 ℃, dropwise adding 25 parts by weight of perfluoropolyether acrylate, 10 parts by weight of methyl methacrylate and 10 parts by weight of n-butyl acrylate, stirring for 1h at the speed of 350r/min to fully pre-emulsify the acrylate monomer, and standing for 1h to fully swell the acrylate monomer. Heating to 75 ℃, adding 10 parts by weight of potassium persulfate at the speed of 200r/min, dissolving the potassium persulfate with water, adding the potassium persulfate within 2 hours, keeping the temperature for 3 hours, cooling to 40 ℃, and discharging to obtain the perfluoropolyether acrylate modified waterborne polyurethane emulsion.
Preparation of water-based polyurethane scale-inhibiting coating
Adding 58 parts by weight of the synthesized perfluoropolyether acrylate modified waterborne polyurethane emulsion into a dispersion pot, heating to 70 ℃, starting stirring, stirring for 1h at the speed of 150r/min, slowly adding 30 parts by weight of alkylated graphene under the stirring condition, adding the alkylated graphene for 0.8h, stirring for 1h, vacuumizing for 1h, and pressurizing with nitrogen for 30min to obtain the waterborne polyurethane scale inhibition coating.
Example 4
Preparation of alkylated graphene
Dispersing 0.1 parts by weight of naphthalene and 0.12 parts by weight of sodium in 50 parts by weight of tetrahydrofuran, and then dispersing 10 parts by weight of graphene nanoplatelets; stirring for 24 hours at room temperature at the stirring speed of 100r/min, then carrying out ultrasonic treatment for 1 hour, adding 15 parts by weight of an alkylating reagent of octadecyl trichlorosilane into a reaction system, and continuously stirring for 24 hours; and finally, respectively adding 10 parts by weight of cyclohexane and 70 parts by weight of deionized water to terminate the alkylation reaction, washing with the deionized water, then filtering with a polytetrafluoroethylene membrane (0.22 mu m), washing a filter cake with the cyclohexane, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the alkylated graphene.
Preparation of perfluoropolyether acrylate modified waterborne polyurethane emulsion
(1) Adding methacryloyl chloride and CH into a three-neck flask2Cl2Triethylamine and polyfluoroether alcohol (added after 30 minutes) are added under the condition of ice-water bath, and the reaction is carried out for 10 hours at room temperature; washing the organic phase with distilled water after the reaction is finished, drying with anhydrous magnesium sulfate, filtering, removing the solvent by rotation, and purifying by column chromatography to obtain colorless oily liquid perfluoropolyether acrylate (methacryloyl chloride, CH)2Cl2The weight ratio of triethylamine to the trimeric fluoroether alcohol is as follows: 3: 10: 30: 30, of a nitrogen-containing gas; the three-mouth bottle and methacryloyl chloride and CH2Cl2Triethylamine and the trifluoroetherol are subjected to drying treatment).
(2) In a reflux condenser pipe, a mechanical stirrer, a thermometer and N2Adding 3 parts by weight of tetrahydrofuran into a protected four-neck flask, heating to 75 ℃ under the stirring of 100r/min, dropwise adding 12 parts by weight of isophorone diisocyanate, heating to 80 ℃, keeping the temperature for 1.5h, adding 2 parts by weight of dimethylolpropionic acid, dissolving the dimethylolpropionic acid in 20 parts by weight of N-methyl pyrrolidone, adding 3 parts by weight of 1, 4-butanediol and dibutyltin dilaurate, keeping the temperature for 3h at 80 ℃, reducing the temperature to 65 ℃, adding 10 parts by weight of 2-hydroxyethyl methacrylate for blocking, and adding 50 parts by weight of acetone during the process to reduce the viscosity of the system. And after 4h, cooling the temperature to 40 ℃, adding 30 parts by weight of triethylamine to neutralize for 0.5h, and adding 70 parts by weight of deionized water at room temperature to emulsify for 1h to obtain the semitransparent bluish waterborne polyurethane seed emulsion. (institute)The tetrahydrofuran is dried under the following conditions: vacuum drying at 90 deg.C and 0.09MPa for 6 h).
(3) In a reflux condenser pipe, a mechanical stirrer, a thermometer and N245 parts by weight of waterborne polyurethane seed emulsion, deionized water and 25 parts by weight of emulsifier (potassium perfluorobutylsulfonate) are added into a protected four-mouth bottle, and stirred at room temperature for 10min at 100 r/min. Heating to 45 ℃, dropwise adding 25 parts by weight of perfluoropolyether acrylate, 10 parts by weight of methyl methacrylate and 10 parts by weight of n-butyl acrylate, stirring for 1h at the speed of 350r/min to fully pre-emulsify the acrylate monomer, and standing for 1h to fully swell the acrylate monomer. Heating to 75 ℃, adding 10 parts by weight of potassium persulfate at the speed of 200r/min, dissolving the potassium persulfate with water, adding the potassium persulfate within 2 hours, keeping the temperature for 3 hours, cooling to 40 ℃, and discharging to obtain the perfluoropolyether acrylate modified waterborne polyurethane emulsion.
Preparation of water-based polyurethane scale-inhibiting coating
Adding 65 parts by weight of the synthesized perfluoropolyether acrylate modified waterborne polyurethane emulsion into a dispersion pot, heating to 70 ℃, starting stirring, stirring for 1h at the speed of 150r/min, slowly adding 10 parts by weight of alkylated graphene under the stirring condition, adding the alkylated graphene for 0.8h, stirring for 1h, vacuumizing for 1h, and pressurizing for 30min with nitrogen to obtain the waterborne polyurethane scale inhibition coating.
Example 5
Preparation of alkylated graphene
Dispersing 0.12 parts by weight of naphthalene and 0.13 parts by weight of sodium in 50 parts by weight of tetrahydrofuran, and then dispersing 20 parts by weight of graphene nanoplatelets; stirring for 24 hours at room temperature at the stirring speed of 100r/min, then carrying out ultrasonic treatment for 1 hour, then dropwise adding 15 parts by weight of an alkylating reagent of octadecyl trichlorosilane into a reaction system, and continuously stirring for 24 hours; and finally, respectively adding 10 parts by weight of cyclohexane and 70 parts by weight of deionized water to terminate the alkylation reaction, washing with the deionized water, then filtering with a polytetrafluoroethylene membrane (0.22 mu m), washing a filter cake with the cyclohexane, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the alkylated graphene.
Preparation of perfluoropolyether acrylate modified waterborne polyurethane emulsion
Adding methacryloyl chloride and CH into a three-neck flask2Cl2Triethylamine and polyfluoroether alcohol (added after 30 minutes) are added under the condition of ice-water bath, and the reaction is carried out for 10 hours at room temperature; washing the organic phase with distilled water after the reaction is finished, drying with anhydrous magnesium sulfate, filtering, removing the solvent by rotation, and purifying by column chromatography to obtain colorless oily liquid perfluoropolyether acrylate (methacryloyl chloride, CH)2Cl2The weight ratio of triethylamine to the trimeric fluoroether alcohol is 4: 10: 35: 32, a first step of removing the first layer; the three-mouth bottle and methacryloyl chloride and CH2Cl2Triethylamine and trifluoroether alcohol were subjected to drying treatment).
In a reflux condenser pipe, a mechanical stirrer, a thermometer and N2Adding 4 parts by weight of tetrahydrofuran into a protected four-neck flask, heating to 75 ℃ under the stirring of 100r/min, dropwise adding 13 parts by weight of isophorone diisocyanate, heating to 82 ℃, keeping the temperature for 1.5h, adding 3 parts by weight of dimethylolpropionic acid, dissolving the dimethylolpropionic acid in 22 parts of N-methyl pyrrolidone, adding 4 parts by weight of 1, 4-butanediol and dibutyltin dilaurate, keeping the temperature for 3h at 82 ℃, reducing the temperature to 65 ℃, adding 15 parts by weight of 2-hydroxyethyl methacrylate for blocking, and adding 50 parts by weight of acetone during the process to reduce the viscosity of the system. And after 4h, cooling the temperature to 40 ℃, adding 35 parts by weight of triethylamine to neutralize for 0.5h, and adding 70 parts by weight of deionized water at room temperature to emulsify for 1h to obtain the semitransparent bluish waterborne polyurethane seed emulsion. (the tetrahydrofuran is dried under the condition of vacuum drying for 6h at 90 ℃ and 0.09 MPa).
In a reflux condenser pipe, a mechanical stirrer, a thermometer and N259 parts by weight of waterborne polyurethane seed emulsion, deionized water and 25 parts by weight of emulsifier (potassium perfluorobutylsulfonate) are added into a protected four-mouth bottle, and stirred at room temperature for 10min at 100 r/min. Heating to 45 ℃, dropwise adding 25 parts by weight of perfluoropolyether acrylate, 10 parts by weight of methyl methacrylate and 10 parts by weight of n-butyl acrylate, stirring for 1h at 350r/min to fully pre-emulsify the acrylate monomer, and standing for 1h to fully swell the acrylate monomer. Heating to 75 ℃, adding at 200r/minAdding 10 parts by weight of potassium persulfate, dissolving the potassium persulfate by using water, adding the potassium persulfate within 2 hours, keeping the temperature for 3 hours, cooling to 40 ℃, and discharging to obtain the perfluoropolyether acrylate modified waterborne polyurethane emulsion.
Preparation of water-based polyurethane scale-inhibiting coating
Adding 78 parts by weight of the synthesized perfluoropolyether acrylate modified waterborne polyurethane emulsion into a dispersion pot, heating to 80 ℃, starting stirring, stirring for 1h at the speed of 150r/min, slowly adding 20 parts by weight of alkylated graphene under the stirring condition, adding the alkylated graphene for 0.8h, stirring for 1h, vacuumizing for 1h, and pressurizing for 30min with nitrogen to obtain the waterborne polyurethane scale inhibition coating.
The performance of the waterborne polyurethane scale inhibition coatings prepared in examples 1-5 was tested, and the test results are shown in table 1.
Table 1 Performance of the waterborne polyurethane scale inhibition coating prepared in examples 1-5
Scale inhibition test
The coatings were subjected to a fouling test in a supersaturated calcium carbonate solution at 60 ℃.
Example 1
Firstly, after the test block is soaked in the solution for 500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, and the test block coated with the coating has no sign of scaling through observation.
② after the test block is soaked in the solution for 1500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, through observation, the test block coated with the coating has a slight calcium carbonate scale layer, and the scaling mass of each square centimeter of test block is 15mg after weighing.
And thirdly, after the test block is soaked in the solution for 3000 hours, taking 1-2 test blocks out, observing the scaling degree of the test block, wherein the test block coated with the coating has a small amount of calcium carbonate scale layer through observation, and the scaling mass of each square centimeter of the test block is 40mg through weighing.
Example 2
Firstly, after the test block is soaked in the solution for 500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, and the test block coated with the coating has no sign of scaling through observation.
② after the test block is soaked in the solution for 1500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, through observation, the test block coated with the coating has a slight calcium carbonate scale layer, and the scaling mass of each square centimeter of test block is 18mg after weighing.
And thirdly, after the test block is soaked in the solution for 3000 hours, taking 1-2 test blocks out, observing the scaling degree of the test block, wherein the test block coated with the coating has a small amount of calcium carbonate scale layer through observation, and the scaling mass of each square centimeter of the test block is 47mg through weighing.
Example 3
Firstly, after the test block is soaked in the solution for 500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, and the test block coated with the coating has no sign of scaling through observation.
② after the test block is soaked in the solution for 1500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, through observation, the test block coated with the coating has a slight calcium carbonate scale layer, and the scaling mass of each square centimeter of test block is 20mg after weighing.
And thirdly, after the test block is soaked in the solution for 3000 hours, taking 1-2 test blocks out, observing the scaling degree of the test block, wherein the test block coated with the coating has a small amount of calcium carbonate scale layer through observation, and the scaling mass of each square centimeter of the test block is 52mg through weighing.
Example 4
Firstly, after the test block is soaked in the solution for 500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, and the test block coated with the coating has no sign of scaling through observation.
② after the test block is soaked in the solution for 1500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, through observation, the test block coated with the coating has a slight calcium carbonate scale layer, and the scaling mass of each square centimeter of test block is 19mg after weighing.
And thirdly, after the test block is soaked in the solution for 3000 hours, taking 1-2 test blocks out, observing the scaling degree of the test block, wherein the test block coated with the coating has a small amount of calcium carbonate scale layer through observation, and the scaling mass of each square centimeter of the test block is 51mg through weighing.
Example 5
Firstly, after the test block is soaked in the solution for 500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, and the test block coated with the coating has no sign of scaling through observation.
② after the test block is soaked in the solution for 1500 hours, 1-2 test blocks are taken out, the degree of scaling is observed, through observation, the test block coated with the coating has a slight calcium carbonate scale layer, and the scaling mass of each square centimeter of test block is 25mg after weighing.
And thirdly, after the test block is soaked in the solution for 3000 hours, taking 1-2 test blocks out, observing the scaling degree of the test block, wherein the test block coated with the coating has a small amount of calcium carbonate scale layer through observation, and the scaling mass of each square centimeter of the test block is 60mg through weighing.
In conclusion, the waterborne polyurethane scale inhibition coating provided by the invention has the advantages that the bonding strength can reach (with steel) 15MPa, the Shore D hardness is 70, the wear resistance is 80mg (1000 g.1000 r) -1, and the water contact angle is 101 degrees; the coating was tested for scale formation in supersaturated calcium carbonate solution at 60 c and when the test block was immersed in the solution for 3000 hours, the minimum scale formation weight per square centimeter of the test block was only 40 mg. Therefore, the waterborne polyurethane scale inhibition coating provided by the invention is not easy to scale, and has high water abrasion resistance, stability and hardness.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The waterborne polyurethane scale inhibition coating comprises the following components in parts by weight: 5-50 parts of alkylated graphene and 20-100 parts of perfluoropolyether acrylate modified aqueous polyurethane emulsion.
2. The scale inhibiting coating of claim 1, wherein the alkyl groups in the alkylated graphene comprise at least one of 1-bromododecyl, octadecyl trichlorosilyl, 1-chlorododecyl, and octadecyl tribromosilyl.
3. The scale inhibition coating of claim 1, wherein the preparation method of the alkylated graphene comprises the following steps:
(I) mixing naphthalene, alkali metal, an organic solvent and graphene, and carrying out reduction reaction to obtain reduced graphene;
(II) mixing the reduced graphene obtained in the step (I) with alkane, and carrying out alkylation reaction to obtain alkylated graphene.
4. The scale inhibition coating as claimed in claim 3, wherein the weight ratio of the alkali metal to the graphene in the step (I) is (0.10-0.20): (5-40).
5. The scale inhibition coating as claimed in claim 3, wherein the weight ratio of the graphene in the step (I) to the alkane in the step (II) is (5-35): 15.
6. the scale inhibiting coating of claim 1, wherein the preparation method of the perfluoropolyether acrylate modified aqueous polyurethane emulsion comprises the following steps:
(1) mixing methacryloyl chloride, trimeric fluoroether alcohol, an acid-binding agent and an organic solvent, and carrying out a first polymerization reaction to obtain perfluoropolyether acrylate;
(2) mixing isophorone diisocyanate, dimethylolpropionic acid, 1, 4-butanediol, a catalyst and an organic solvent, and carrying out a second polymerization reaction to obtain waterborne polyurethane;
(3) emulsifying the waterborne polyurethane obtained in the step (2) with water to obtain waterborne polyurethane seed emulsion;
(4) mixing the perfluoropolyether acrylate obtained in the step (1) and the aqueous polyurethane seed emulsion obtained in the step (3) with water, an emulsifier, methyl methacrylate, n-butyl acrylate and an initiator, and carrying out a third polymerization reaction to obtain a perfluoropolyether acrylate modified aqueous polyurethane emulsion;
the steps (1) and (2) are not limited in sequence.
7. The scale inhibition coating as claimed in claim 6, wherein the weight ratio of the methacryloyl chloride to the trifluoroether alcohol in the step (1) is (2-8): (40-50).
8. The scale inhibition coating of claim 6, wherein the weight ratio of isophorone diisocyanate, dimethylolpropionic acid and 1, 4-butanediol in step (2) is (10-17): (1-7): (1-8).
9. The scale inhibition coating of claim 6, wherein the weight ratio of the perfluoropolyether acrylate, the aqueous polyurethane seed emulsion, the methyl methacrylate and the n-butyl acrylate in the step (4) is (10-35): (17-65): (5-60): (5-60).
10. The preparation method of the waterborne polyurethane scale inhibition coating of any one of claims 1 to 9, which comprises the following steps:
and mixing the alkylated graphene and the perfluoropolyether acrylate modified aqueous polyurethane emulsion to obtain the aqueous polyurethane scale inhibition coating.
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