CN105419620A - Modified polyurethane resin coating and preparation method thereof - Google Patents
Modified polyurethane resin coating and preparation method thereof Download PDFInfo
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- CN105419620A CN105419620A CN201510899714.5A CN201510899714A CN105419620A CN 105419620 A CN105419620 A CN 105419620A CN 201510899714 A CN201510899714 A CN 201510899714A CN 105419620 A CN105419620 A CN 105419620A
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- coating
- modified polyurethane
- polyurethane resin
- diisocyanate
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- 239000011248 coating agent Substances 0.000 title claims abstract description 46
- 238000000576 coating method Methods 0.000 title claims abstract description 46
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 12
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract 5
- 235000011037 adipic acid Nutrition 0.000 claims abstract 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 12
- 239000012964 benzotriazole Substances 0.000 claims description 12
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000002114 nanocomposite Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims 2
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 239000013535 sea water Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- -1 di-n-butyltin diester Chemical class 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 229920000180 alkyd Polymers 0.000 abstract 1
- 235000019439 ethyl acetate Nutrition 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 abstract 1
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000004159 Potassium persulphate Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Diphosphoinositol tetrakisphosphate Chemical compound OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000005406 washing 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a modified polyurethane resin coating, which is made from raw materials with parts by weight: toluene diisocynate 60-80 parts, dicyclohexylmethane diisocyanate 5-10 parts, hexamethylene diisocyanate 5-10 parts, hexanedioic acids 4-8 parts, alkyd resins 1-5 parts, epoxy resins 2-4 parts, propylene glycol 1-3 parts, methyldiethanolamine 1-3 parts, di-n-butyltin diester 1-4 parts, acetic ethers 5-10 parts, phosphoric acids 0.5-1 part, deionized water 10-30 parts and polymer nanoparticles 8-16 parts. The modified polyurethane resin coating combines the polymer nanoparticles and a coating, disperses in modified polyurethane resins, forms an effective corrosion resistant composite coating, and has the excellent performance of oil resistivity, seawater resistant, wear resistance and impact resistance and the like.
Description
Technical field
The present invention relates to a kind of modified polyurethane resin coating and preparation method thereof.
Background technology
The Water-borne modification of urethane resin progressively replaces solvent-borne type, becomes the important directions of polyurethane industrial development.Urethane can be widely used in coating, tackiness agent, fabric coating and finishing composition, hide finishes, sheet surface treating agent and Fiber strength agent.Aqueous polyurethane emulsion is not only the coating comparing environmental protection, and has oil-proofness, sea water resistance, the premium properties such as wear-resistant and shock-resistant.Existingly formulating of recipe carried out to urethane and adjusts the requirement that uses with satisfied reality, and high performance aqueous polyurethane can be prepared by combining nano hybridization technique.Be main film forming matter with urethane or modified polyurethane, add appropriate auxiliary film forming matter component, the coating of auxiliary agent solvent is generally polyurethane coating.Polyurethane resin coating has and is obviously better than the specific of other coating, and the advantage of polyurethane coating is that paint film wear resistance is strong, and decorate properties is good, film adhesive is strong, and be coated with film elasticity high, film corrosion resistance nature is strong, bake out temperature wide ranges, high temperature resistant low-temperature performance is given prominence to, excellent insulation performance, assortment are many, but it also has obvious shortcoming, such as guarantor's light tint retention is poor, resin emulsion poor stability, easy damage coating, construction requirement is high.
When being applied to metallurgical metal process, the coating formed easily is corroded and produces destruction, if when such as metallic copper is in the etchant solution containing ion (such as chlorion, sulfate ion etc.), easily there is spot corrosion and (namely occur the corrosion aperture of developing in depth and breadth in local, metallic surface.Facts have proved in a large number; the anticorrosion ability of hybrid corrosion inhibitor benzotriazole and its derivative to copper is more satisfactory; Application comparison is extensive; its mechanism of action is the complex compound protective membrane that can form one deck benzotriazole and cupric ion on copper surface; and can in anode film forming; also at cathode filming, water and oxygen in water can be stoped to the diffusion of metallic surface, reduce the corrosion speed of copper.
As previously mentioned, along with the change of extraneous corrosive medium, need inhibiter to be discharged into longer by corrosion failure region, comparing effective means is directly joined by inhibiter in metal treatment coating, the effect of physical barrier that what coating mainly played is.But; this method of directly mixing sometimes can not play enough provide protections; inhibiter directly contacts with coating; in most of the cases; this system does not possess the ability of stimulating responsive release inhibiter; if when inhibiter solubleness is in the coating higher, the inhibiter of release fast can make coating generation foaming phenomena, and can destroy the integrity of coating.
Summary of the invention
The object of the present invention is to provide a kind of modified polyurethane resin coating, previously prepared good load is coated with the nanoparticle dispersion of inhibiter in urethane resin by it, thus coated for support materials inhibiter is mixed in coating, the loss that these carriers not only can avoid inhibiter unnecessary, and inhibiter directly destroys coating, and there is certain environment stimulating responsive, such as physical disturbance, PH change and illumination etc.
Technical scheme of the present invention is: a kind of modified polyurethane resin coating, described coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, hexanodioic acid 4-8 part, Synolac 1-5 part, epoxy resin 2-4 part, propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part, vinyl acetic monomer 5-10 part, phosphoric acid 0.5-1 part, deionized water 10-30 part; And polymer nano-particle 8-16 part.
The preparation method of this coating is as follows:
1) tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, vinyl acetic monomer 5-10 part are added reactor, stirrer is used fully to stir, be warming up to 90-100 DEG C, slowly add hexanodioic acid 4-8 part;
2) continue to add Synolac 1-5 part, epoxy resin 2-4 part, fully stir more than 1h,
3) chainextender, activator and catalyzer is added: add propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part according to dividing equally four minor tick 30min, phosphoric acid 0.5-1 part, then be incubated 80 degrees Celsius of more than 4h, add ionized water and carry out more than emulsification 30min;
4) polymer nano-particle being coated with benzotriazole is mixed in above-mentioned emulsion by ultrasonic disperse, at insulation 50 DEG C of abundant more than stirring reaction 1h, obtains modified polyurethane resin-Nanocomposites coating.
Compared with prior art, the coated inhibiter of polymer nano granules of the present invention, this polymer nano granules can in corrosive medium, there is pH value responsiveness, in external stimulus coating or when damaging coating, due to the soda acid change of corrosion local, inhibiter is discharged according to situation difference, in metallic surface absorption film-forming, play the effect of initiatively reparation, the polymer nano-particle that the multi-step emulsion polymerization that the present invention simultaneously adopts obtains coated inhibiter has superior coated function and stability, yield rate is higher, polymer nano-particle is combined with coating, be scattered in modified polyurethane resin, form effective corrosion-resistant composite coating, there is oil-proofness, sea water resistance, the premium properties such as wear-resistant and shock-resistant.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
A kind of modified polyurethane resin-Nanocomposites coating, described coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, hexanodioic acid 4-8 part, Synolac 1-5 part, epoxy resin 2-4 part, propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part, vinyl acetic monomer 5-10 part, phosphoric acid 0.5-1 part, deionized water 10-30 part; And polymer nano-particle 8-16 part.
The preparation method of this coating is as follows:
1) tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, vinyl acetic monomer 5-10 part are added reactor, stirrer is used fully to stir, be warming up to 90-100 DEG C, slowly add hexanodioic acid 4-8 part;
2) continue to add Synolac 1-5 part, epoxy resin 2-4 part, fully stir more than 1h,
3) chainextender, activator and catalyzer is added: add propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part according to dividing equally four minor tick 30min, phosphoric acid 0.5-1 part, then be incubated 80 degrees Celsius of more than 4h, add ionized water and carry out more than emulsification 30min;
4) polymer nano-particle being coated with benzotriazole is mixed in above-mentioned emulsion by ultrasonic disperse, at insulation 50 DEG C of abundant more than stirring reaction 1h, obtains modified polyurethane resin-Nanocomposites coating.
This preparation method being coated with the polymer nano-particle of benzotriazole is as follows:
Step 1): by n-butyl acrylate 2.5 weight part (or gram), methyl methacrylate 1.1 weight part, methacrylic acid 0.4 weight part, the mix monomer of myo-Inositol hexaphosphate 0.25 weight part joins in the reaction vessel of 1L capacity, then Potassium Persulphate 0.23 weight part will be contained according in every premium on currency, the aqueous solution 200ml that sodium lauryl sulphate 0.22 weight ratio obtains adds in reactor, pass into nitrogen in the reactor, temperature is increased to 85-90 DEG C, permanent magnet direct current motor is used to carry out mechanic whirl-nett reaction 24-36 hour, obtain primary emulsion,
Step 2): the aqueous solution 150mL containing Potassium Persulphate 0.2 weight part, sodium lauryl sulphate 0.45 weight part is joined in above-mentioned primary emulsion, then slowly butyl acrylate 2 weight part, methyl methacrylate 30 weight part is instilled, the mix monomer of methacrylic acid 14 weight part, time for adding is 40min, temperature of reaction remains on 85-90 DEG C, use permanent magnet direct current motor to carry out mechanic whirl-nett reaction 8 hours, obtain one-level core emulsion; Configuration quality concentration be 4% benzotriazole aqueous solution 400ml be placed in another reactor (capacity can be 1L), the one-level core emulsion 50ml getting above-mentioned synthesis joins in the benzotriazole aqueous solution, temperature is increased to 85-90 DEG C, keep more than 3h, obtain the one-level core emulsion being adsorbed with a certain amount of benzotriazole.
Step 3): 0.5 weight part Potassium Persulphate is joined the above-mentioned one-level core emulsion containing being adsorbed with a certain amount of benzotriazole, slowly instill butyl acrylate 3.8 weight part, methyl methacrylate 40 weight part subsequently, the mix monomer of methacrylic acid 2 weight part, drip process lasts 40min, temperature of reaction remains on 85-90 DEG C, sustained reaction is more than 8h at least, obtains the secondary core emulsion being coated with benzotriazole;
Step 4): the secondary core emulsion 100ml getting above-mentioned synthesis, add the aqueous solution 200ml containing 0.2 weight part Potassium Persulphate, temperature of reaction remains on 85-90 DEG C, the speed being 0.04g/min according to rate of addition slowly instills vinylbenzene 0.5 weight part, then about using aqueous sodium hydroxide solution (10wt%) to regulate the pH value to 10 of reaction soln, finally again slowly instill vinylbenzene 15 weight part, time for adding is no less than 40min, constant temperature keeps 85-90 DEG C and continues at least 8 hours, be separated by whizzer after completing above-mentioned steps, first use absolute ethanol washing twice, after use deionized water wash more than three times, be placed in dry 24 hours of the air dry oven of 50 DEG C, obtain the polymer nano-particle being coated with benzotriazole.
Embodiment 1
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60 parts, dicyclohexyl methane diisocyanate 5 parts, hexamethylene diisocyanate 5 parts, hexanodioic acid 4 parts, Synolac 1 part, epoxy resin 2 parts, propylene glycol 1 part, methyldiethanolamine 1 part, dibutyl tin diacetate 1 part, vinyl acetic monomer 6 parts, phosphoric acid 0.5 part, deionized water 15 parts; And polymer nano-particle 8 parts.Preparation method as previously mentioned.
Embodiment 2
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 70 parts, dicyclohexyl methane diisocyanate 10 parts, hexamethylene diisocyanate 10 parts, hexanodioic acid 8 parts, Synolac 3 parts, epoxy resin 4 parts, propylene glycol 3 parts, methyldiethanolamine 2 parts, dibutyl tin diacetate 4 parts, vinyl acetic monomer 10 parts, phosphoric acid 0.5 part, deionized water 30 parts; And polymer nano-particle 10 parts.Preparation method as previously mentioned.
Embodiment 3
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60 parts, dicyclohexyl methane diisocyanate 8 parts, hexamethylene diisocyanate 7 parts, hexanodioic acid 5 parts, Synolac 4 parts, epoxy resin 4 parts, propylene glycol 3 parts, methyldiethanolamine 1 part, dibutyl tin diacetate 3 parts, vinyl acetic monomer 5 parts, phosphatase 11 part, deionized water 25 parts; And polymer nano-particle 12 parts.Preparation method as previously mentioned.
Embodiment 4
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 80 parts, dicyclohexyl methane diisocyanate 10 parts, hexamethylene diisocyanate 8 parts, hexanodioic acid 8 parts, Synolac 5 parts, epoxy resin 4 parts, propylene glycol 2 parts, methyldiethanolamine 3 parts, dibutyl tin diacetate 1 part, vinyl acetic monomer 6 parts, phosphatase 11 part, deionized water 30 parts; And polymer nano-particle 14 parts.Preparation method as previously mentioned.
Embodiment 5
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60 parts, dicyclohexyl methane diisocyanate 8 parts, hexamethylene diisocyanate 5 parts, hexanodioic acid 6 parts, Synolac 2 parts, epoxy resin 2 parts, propylene glycol 2 parts, methyldiethanolamine 3 parts, dibutyl tin diacetate 4 parts, vinyl acetic monomer 10 parts, phosphoric acid 0.5 part, deionized water 25 parts; And polymer nano-particle 16 parts.Preparation method as previously mentioned.
The coating obtained by above-described embodiment 1-5 carries out surface treatment to same metal works, and efficacy parameter is compared as follows:
Embodiment 1-5 the performance test results comparative analysis table
Although give detailed description and explanation to the specific embodiment of the present invention above; but what should indicate is; we can carry out various equivalence according to conception of the present invention to above-mentioned embodiment and change and amendment; its function produced do not exceed that specification sheets contains yet spiritual time, all should within protection scope of the present invention.Such as, weight part can be chosen as gram or other weight unit.The above; be only preferred embodiment of the present invention; not in order to limit the present invention, every above embodiment is done according to technical spirit of the present invention any trickle amendment, equivalently replace and improve, within the protection domain that all should be included in technical solution of the present invention.
Claims (2)
1. a modified polyurethane resin coating, described coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, adipic acid 4-8 part, Synolac 1-5 part, epoxy resin 2-4 part, propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part, vinyl acetic monomer 5-10 part, phosphoric acid 0.5-1 part, deionized water 10-30 part; And polymer nano-particle 8-16 part.
2. the preparation method of a modified polyurethane resin coating as claimed in claim 1 is as follows:
1) tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, vinyl acetic monomer 5-10 part are added reactor, stirrer is used fully to stir, be warming up to 90-100 DEG C, slowly add adipic acid 4-8 part;
2) continue to add Synolac 1-5 part, epoxy resin 2-4 part, fully stir more than 1h,
3) chainextender, activator and catalyzer is added: add propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part according to dividing equally four minor tick 30min, phosphoric acid 0.5-1 part, then be incubated 80 degrees Celsius of more than 4h, add ionized water and carry out more than emulsification 30min;
4) polymer nano-particle being coated with benzotriazole is mixed in above-mentioned emulsion by ultrasonic disperse, at insulation 50 DEG C of abundant more than stirring reaction 1h, obtains modified polyurethane resin-Nanocomposites coating.
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| CN110563918A (en) * | 2019-09-02 | 2019-12-13 | 福建国邦新材料有限公司 | Preparation method of modified grafted polyurethane resin |
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