WO2023202240A1 - 耐盐雾聚天门冬氨酸酯的制备方法、耐盐雾聚天门冬氨酸酯及涂料 - Google Patents
耐盐雾聚天门冬氨酸酯的制备方法、耐盐雾聚天门冬氨酸酯及涂料 Download PDFInfo
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- WO2023202240A1 WO2023202240A1 PCT/CN2023/079616 CN2023079616W WO2023202240A1 WO 2023202240 A1 WO2023202240 A1 WO 2023202240A1 CN 2023079616 W CN2023079616 W CN 2023079616W WO 2023202240 A1 WO2023202240 A1 WO 2023202240A1
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- WIPO (PCT)
- Prior art keywords
- polyaspartate
- resistant
- salt spray
- component
- salt
- Prior art date
Links
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 121
- 239000007921 spray Substances 0.000 title claims abstract description 59
- 238000000576 coating method Methods 0.000 title claims abstract description 48
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 39
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 39
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 39
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 7
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims description 24
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 4
- -1 tetrakis titanate Isopropyl ester Chemical class 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000010276 construction Methods 0.000 abstract description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000003335 secondary amines Chemical group 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical group O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000020226 cashew nut Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- LVASCWIMLIKXLA-CABCVRRESA-N 7-bromo-6-chloro-3-[3-[(2r,3s)-3-hydroxypiperidin-2-yl]-2-oxopropyl]quinazolin-4-one Chemical compound O[C@H]1CCCN[C@@H]1CC(=O)CN1C(=O)C2=CC(Cl)=C(Br)C=C2N=C1 LVASCWIMLIKXLA-CABCVRRESA-N 0.000 description 1
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229940009098 aspartate Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 235000010300 dimethyl dicarbonate Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/329—Hydroxyamines containing aromatic groups
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C09D175/02—Polyureas
-
- 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
Definitions
- the present application relates to the field of polyaspartic acid esters, and in particular to a preparation method of salt spray-resistant polyaspartic acid esters, salt spray-resistant polyaspartic acid esters and coatings.
- Polyaspartic acid ester resin is produced by the Michael reaction of aliphatic or alicyclic diamine or polyamine and maleate or fumarate. Polyaspartate is usually used in the field of coatings. Polyaspartate coatings are made by mixing and reacting polyaspartate and isocyanate. Compared with ordinary amino resins, polyaspartate resin and The reaction rate of isocyanate is slower. The reason is that maleate or fumarate has steric hindrance and induction effects, which can effectively delay the reaction rate of polyaspartate resin and isocyanate. Therefore, the polyaspartate produced Acid ester coating has a longer construction time, and its coating construction methods can be spraying, roller coating, scraping, etc., without the need for professional and expensive construction equipment.
- polyaspartate coatings are high-solid environmentally friendly coatings and are widely used in waterproofing, flooring, and anti-corrosion fields.
- polyaspartate coatings are difficult to promote and apply in heavy anti-corrosion fields such as engineering machinery anti-corrosion and ship anti-corrosion.
- this application provides a preparation method of salt spray-resistant polyaspartate, salt spray-resistant polyaspartate and coatings.
- this application provides a preparation method for salt spray-resistant polyaspartate, adopting the following technical solution:
- a preparation method of salt spray-resistant polyaspartate including the following steps:
- cardanol is a unique natural phenolic material extracted through the distillation of cashew nut shell oil. Its molecule includes an aromatic ring, hydroxyl group and a long aliphatic side chain.
- the aromatic ring can provide good resistance to Chemical properties and rigidity.
- the hydroxyl group can provide reactivity, allowing it to undergo esterification or transesterification reactions.
- the aliphatic side chain can provide excellent water resistance, toughness, low viscosity and long construction period. Therefore, through cashew nuts Phenol resin modified polyaspartate can improve the water resistance and salt spray resistance of polyaspartate resin, giving polyaspartate resin excellent corrosion resistance.
- the polyaspartate resin produced has low viscosity, has a longer construction time, can be constructed without adding solvents, and is green and environmentally friendly.
- the catalyst mainly plays the role of transesterification, carrying out transesterification reaction between cardanol resin and polyaspartic acid ester, connecting cardanol resin to polyaspartic acid ester and displacing the monohydric alcohol at the same time.
- Tetraisopropyl titanate easily absorbs water and generates titanium oxide, which is beneficial to improving the anti-corrosion ability of the coating.
- Dibutyltin oxide has thermal stability and hydrolysis resistance. The product is neutral and has no corrosive effect.
- the two catalysts do not need to be separated after the reaction is completed, and do not affect product quality, saving process costs.
- the polyaspartate is one or a combination of F420, F520, F530, F540, F2850 and F524.
- the polyaspartate is F420 and/or F520.
- the amines used to synthesize F420 and F520 are HMDA and DMDC. They have no benzene ring structure in the molecules, have better weather resistance, and the reaction speed is slower than other amines, so they have a longer coating pot life. , the bicyclohexyl structure can also bring higher hardness to polyaspartate.
- the polyaspartate is F520.
- the cardanol resin uses NX-202X series cardanol or LITE-2020.
- LITE-2020 The structural formula of LITE-2020 is:
- this application provides a salt spray-resistant polyaspartate, adopting the following technical solution:
- a salt spray-resistant polyaspartic acid ester is prepared by the preparation method of the salt spray-resistant polyaspartic acid ester described in the above technical solution.
- the polyaspartate produced has excellent salt spray resistance and water resistance, low viscosity, and long operation time during construction.
- this application provides a salt spray-resistant polyaspartate coating, which adopts the following technical solution:
- a salt spray-resistant polyaspartate coating is composed of two components, component A and component B, which are mixed and solidified at room temperature.
- the component A at least includes the salt spray-resistant polyaspartate coating described in the above technical solution.
- Aspartate, the B component is an isocyanate curing agent.
- the coating formed by applying the coating of the present application has excellent corrosion resistance, high hardness, long curing time after mixing component A and component B, and longer construction operation time.
- the A component also includes dispersant, anti-settling agent, defoaming agent, barium sulfate, titanium One or more of white powder, zinc phosphate, leveling agent, butyl acetate.
- the isocyanate curing agent is HDI trimer.
- This application uses cardanol resin to modify polyaspartic acid ester.
- the aromatic ring in the cardanol resin molecule can provide good chemical resistance and rigidity, and the hydroxyl group can provide reactivity, allowing it to be esterified or Through transesterification reaction, the aliphatic side chain can provide excellent water resistance, toughness, low viscosity and long construction period.
- the cardanol resin modified polyaspartate can improve the polyester exchange rate.
- the water resistance and salt spray resistance of aspartic acid ester resin make polyaspartic acid ester resin have excellent corrosion resistance.
- the obtained polyaspartic acid ester resin also has low viscosity, long construction time and no It can be constructed without adding solvent.
- the polyaspartate produced by this application has excellent water resistance and salt spray resistance, low viscosity, and long operation time during construction.
- the coating formed by applying the coating of this application has excellent corrosion resistance, high hardness, long curing time after mixing component A and component B, and longer construction operation time.
- Polyaspartate is a high-solid environmentally friendly coating with small molecular weight and low viscosity that can be applied without adding solvents. It is widely used in waterproofing, flooring, and anti-corrosion fields. But also because of its points The molecular weight is small and the ester bond content in the molecule is high. The hydrophobicity and water resistance of the polyaspartate coating obtained after reacting with isocyanate is poor, and the salt spray itself is in a supersaturated water mist state. Polyaspartate The poor hydrophobicity and water resistance of acid ester coatings will make it easier for salt spray to penetrate the paint film and cause corrosion. Therefore, the salt spray resistance of polyaspartate coatings is usually poor. It is used in important projects such as engineering machinery anti-corrosion and ship anti-corrosion. It is difficult to popularize and apply in the field of anti-corrosion.
- the secondary amine group equivalent of the obtained salt spray-resistant polyaspartate was 263.5, and the viscosity was 1800 mPa ⁇ s (25°C).
- the obtained salt spray-resistant polyaspartate had a secondary amine group equivalent of 321 and a viscosity of 3350 mPa ⁇ s (25°C).
- the obtained salt spray-resistant polyaspartate had a secondary amine group equivalent of 309 and a viscosity of 3200 mPa ⁇ s (25°C).
- the obtained salt spray-resistant polyaspartate had a secondary amine group equivalent of 350 and a viscosity of 4100 mPa ⁇ s (25°C).
- F420 polyaspartate (Shenzhen Feiyang Junyan New Materials Co., Ltd.) has a secondary amine group equivalent of 277 and a viscosity of 1000 mPa ⁇ s (25°C).
- F520 polyaspartate (Shenzhen Feiyang Junyan New Materials Co., Ltd.) has a secondary amine group equivalent of 291 and a viscosity of 1300 mPa ⁇ s (25°C).
- Example 2 The difference from Example 2 is that the added amount of LITE-2020 cardanol resin is 22.9g (0.06mol).
- Example 2 The difference from Example 2 is that the added amount of LITE-2020 cardanol resin is 133.5g (0.35mol).
- the polyaspartic acid ester prepared in Examples 1-4 and Comparative Examples 1-4 is used to prepare the polyaspartic acid ester coating according to the following weight parts ratio.
- the specific ratio is in Table 2:
- the dispersant is DISPERBYK-163 from BYK, Germany
- the anti-settling agent is fumed silica from WACKER, Germany.
- the defoaming agent is BYK-1790 from BYK, Germany
- the leveling agent is EFKA-3600 from BASF, Germany
- the barium sulfate particle size is 2200 mesh
- the titanium dioxide is NTR606 from Ningbo Xinfu
- the zinc sulfate is Nubirox- from Spain. 213.
- the isocyanate curing agent is Wanhua Chemical's HT-100 (HDI trimer, the mass fraction of isocyanate (—NCO) is 21.7%).
- the preparation method of polyaspartate coating is as follows:
- the detection method refers to GB/T31416-2015;
- the detection method refers to GB/T1728-1989;
- Adhesion The detection method refers to GB/T9286-1998;
- the testing method refers to GB/T6739-2006;
- Salt spray resistance The testing method refers to GB/T1771-2007.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
一种耐盐雾聚天门冬氨酸酯的制备方法、耐盐雾聚天门冬氨酸酯及涂料。耐盐雾聚天门冬氨酸酯的制备方法包括以下步骤：将聚天门冬氨酸酯、腰果酚树脂及催化剂混合于一起进行酯交换反应，控制温度为100～130℃，控制相对真空度为-0.095-0.1 Mpa，搅拌反应2～5小时得到耐盐雾聚天门冬氨酸酯；其中，所述聚天门冬氨酸酯、腰果酚树脂及催化剂的摩尔比为聚天门冬氨酸酯：腰果酚树脂：催化剂=1：0.1～0.3：0.001～0.003，所述催化剂为钛酸四异丙酯或二丁基氧化锡。制得的聚天门冬氨酸酯具有优异的耐水性和耐盐雾性能，且粘度低，施工时可操作时间长。
Description
本申请涉及聚天门冬氨酸酯领域，尤其是涉及一种耐盐雾聚天门冬氨酸酯的制备方法、耐盐雾聚天门冬氨酸酯及涂料。
聚天门冬氨酸酯树脂是脂肪族或脂环族的二元胺或多元胺与马来酸酯或富马酸酯进行迈克尔反应制得。聚天门冬氨酸酯通常应用于涂料领域，通过将聚天门冬氨酸酯与异氰酸酯混合反应制成聚天门冬氨酸酯涂料，相比于一般的氨基树脂，聚天门冬氨酸酯树脂与异氰酸酯反应速度更慢，其原因在于马来酸酯或者富马酸酯存在空间位阻及诱导效应，能有效延缓聚天门冬氨酸酯树脂与异氰酸酯的反应速度，因此制得的聚天门冬氨酸酯涂料有更长的施工时间，其涂料施工方式可以为喷涂、滚涂、刮涂等，无需专业昂贵的施工设备。
聚天门冬氨酸酯仲胺基的反应活性比一般的聚氨酯树脂的羟基反应活性更高，反应速度要快很多，能实现快速固化，无需烘烤加热固化的特点。此外，聚天门冬氨酸酯的分子量小，粘度低能做到无需添加溶剂便可以施工。因此，聚天门冬氨酸酯涂料属于高固体份环保型的涂料，广泛的应用在防水，地坪，防腐领域。
但是聚天门冬氨酸酯的分子量小，分子中酯键含量高，与异氰酸酯反应之后制得的聚天门冬氨酸酯涂料的疏水性及耐水性不佳，导致涂料的耐盐雾性能也比较差，主要是由于盐雾本身为过饱和的水雾状态，聚天门冬氨酸酯涂料疏水性及耐水性的不佳会导致盐雾更容易渗透漆膜并造成腐
蚀，因此受限于耐盐雾性能的不佳，聚天门冬氨酸酯涂料在工程机械防腐，船舶防腐等重防腐领域难以推广应用。
发明内容
为了改善聚天门冬氨酸酯的耐盐雾性能，本申请提供一种耐盐雾聚天门冬氨酸酯的制备方法、耐盐雾聚天门冬氨酸酯及涂料。
第一方面，本申请提供一种耐盐雾聚天门冬氨酸酯的制备方法，采用如下的技术方案：
一种耐盐雾聚天门冬氨酸酯的制备方法，包括以下步骤：
将聚天门冬氨酸酯、腰果酚树脂及催化剂混合于一起进行酯交换反应，控制温度为100～130℃，控制相对真空度为-0.095～-0.1MPa，搅拌反应2～5小时得到耐盐雾聚天门冬氨酸酯；
其中，所述聚天门冬氨酸酯、腰果酚树脂及催化剂的摩尔比为聚天门冬氨酸酯：腰果酚树脂：催化剂＝1：0.1～0.3：0.001～0.003，所述催化剂为钛酸四异丙酯或二丁基氧化锡；
所述腰果酚树脂的结构式为：
通过采用上述技术方案，腰果酚是通过腰果壳油精馏提取的一种独特的天然酚醛材料，其分子包括一个芳香环、羟基和一个长的脂肪族侧链组成，芳香环可提供良好的耐化学品性能和刚性，羟基能够提供反应活性，使其能够进行酯化或者酯交换反应，脂肪族侧链能够提供优异的耐水性能、韧性、低粘度以及长的施工期的特点，因此，通过腰果酚树脂改性聚天门冬氨酸酯能够提升聚天门冬氨酸酯树脂的耐水性和耐盐雾性能，使聚天门冬氨酸酯树脂具有优异的耐腐蚀性能。
另外，由于腰果酚树脂的低粘度特点，使制得的聚天门冬氨酸酯树脂粘度低，具有更长的施工时间且不需要添加溶剂就能施工，绿色环保。
催化剂主要起酯交换的作用，将腰果酚树脂与聚天门冬氨酸酯进行酯交换反应，将腰果酚树脂接在聚天门冬氨酸酯上并同时置换出一元醇。钛酸四异丙酯极易吸水生成氧化钛，有利于提高涂层的防腐能力。二丁基氧化锡具有热稳定性及抗水解性，产品呈中性，无腐蚀作用。另外，该两种催化剂在反应完毕后无需进行分离操作，且不影响产品质量，节省工艺成本。
经试验验证，当腰果酚树脂与聚天门冬氨酸酯的摩尔比小于0.1：1时，制得的聚天门冬氨酸酯树脂的耐盐雾提升不明显，而随着腰果酚树脂添加量的增加，制得的聚天门冬氨酸酯的耐盐雾性能也逐渐提升，但树脂的粘
度也越大，应用的时候需要添加越多的溶剂，当腰果酚树脂与聚天门冬氨酸酯的摩尔比大于0.3：1时，制得的聚天门冬氨酸酯树脂的硬度会降低，漆膜容易受损，而且腰果酚树脂添加量太多，支链太长，聚天门冬氨酸酯后续应用时与固化剂的交联密度会降低，耐盐雾效果会下降。
优选的，所述聚天门冬氨酸酯为F420、F520、F530、F540、F2850、F524中的一种或多种的组合。
优选的，所述聚天门冬氨酸酯为F420和/或F520。
通过采用上述技术方案，用于合成F420及F520的胺是HMDA及DMDC，分子中没有苯环结构，耐候性更好，反应速度相比其他的胺类更慢，因此有更长的涂料适用期，双环己基结构给也能够给聚天门冬氨酸酯带来更高的硬度。
优选的，所述聚天门冬氨酸酯为F520。
具体而言，所述腰果酚树脂采用NX-202X系列腰果酚或LITE-2020。
所述NX-202X系列腰果酚的结构式为：
所述LITE-2020的结构式为：
优选的，所述聚天门冬氨酸酯、腰果酚树脂及催化剂的摩尔比为聚天门冬氨酸酯：腰果酚树脂：催化剂＝1：0.25：0.002。
经试验验证，该配比下，制得的耐盐雾聚天门冬氨酸酯综合性能更好，应用至聚天门冬氨酸酯涂料时，涂料的应用表现更好。
第二方面，本申请提供一种耐盐雾聚天门冬氨酸酯，采用如下的技术方案：
一种耐盐雾聚天门冬氨酸酯，由上述技术方案中所述的耐盐雾聚天门冬氨酸酯的制备方法制得。
通过采用上述技术方案，制得的聚天门冬氨酸酯具有优异的耐盐雾性能和耐水性，且粘度低，施工时可操作时间长。
第三方面，本申请提供一种耐盐雾聚天门冬氨酸酯涂料，采用如下的技术方案：
一种耐盐雾聚天门冬氨酸酯涂料，由A组分和B组分两种组分在室温下混合固化成型，所述A组分至少包括上述技术方案中所述的耐盐雾聚天门冬氨酸酯，所述B组分为异氰酸酯固化剂。
通过采用本申请涂料涂覆形成的涂层耐腐蚀性能优异，硬度高，A组分与B组分混合后固化时间长，具有更长的施工操作时间。
优选的，所述A组分还包括分散剂、防沉剂、消泡剂、硫酸钡、钛
白粉、磷酸锌、流平剂、醋酸丁酯中的一种或多种。
优选的，所述A组分与B组分的质量比按A组分中仲胺基当量：B组分中异氰酸酯基当量＝1：1.05计。
通过采用上述技术方案，异氰酸酯固化剂的过量添加可保证聚天门冬氨酸酯充分反应。
优选的，所述异氰酸酯固化剂为HDI三聚体。
综上所述，本申请包括以下至少一种有益技术效果：
1、本申请通过腰果酚树脂对聚天门冬氨酸酯进行改性，腰果酚树脂分子中芳香环可提供良好的耐化学品性能和刚性，羟基能够提供反应活性，使其能够进行酯化或者酯交换反应，脂肪族侧链能够提供优异的耐水性能、韧性、低粘度以及长的施工期的特点，结合催化的交联催化作用，通过腰果酚树脂改性聚天门冬氨酸酯能够提升聚天门冬氨酸酯树脂的耐水性和耐盐雾性能，使聚天门冬氨酸酯树脂具有优异的耐腐蚀性能，制得的聚天门冬氨酸酯树脂还具有粘度低，施工时间长且不需要添加溶剂就能施工的特点。
2、本申请制得的聚天门冬氨酸酯具有优异的耐水性和耐盐雾性能，且粘度低，施工时可操作时间长。
3、采用本申请涂料涂覆形成的涂层耐腐蚀性能优异，硬度高，A组分与B组分混合后固化时间长，具有更长的施工操作时间。
聚天门冬氨酸酯是一种分子量小，粘度低，无需添加溶剂便可以施工的高固体份环保型涂料，广泛应用于防水、地坪、防腐领域。但也因其分
子量小，分子中酯键含量高，与异氰酸酯反应之后制得的聚天门冬氨酸酯涂料的疏水性及耐水性不佳，而盐雾本身为过饱和的水雾状态，聚天门冬氨酸酯涂料疏水性及耐水性的不佳会导致盐雾更容易渗透漆膜并造成腐蚀，因此聚天门冬氨酸酯涂料的耐盐雾性能通常比较差，在工程机械防腐，船舶防腐等重防腐领域难以推广应用。
基于上述问题，本申请人经过大量研究发现，采用腰果酚与聚天门冬氨酸酯进行酯化反应得到的改性聚天门冬氨酸酯具有优异的耐水性和耐盐雾性能，应用到涂料上具有优异的耐腐蚀性能。本申请正是基于上述发现作出的。
为了更方便理解本申请的技术方案，以下结合表格和实施例对本申请作进一步详细说明，但不作为本申请限定的保护范围。
实施例
实施例1
取1L的四口烧瓶，加入F530聚天门冬氨酸酯514g(1mol)，NX-2024腰果酚树脂30.2g(0.1mol)，钛酸四异丙酯0.3g(0.001mol)，然后搅拌升温至100℃，在相对真空度为-0.095MPa下减压蒸馏反应2小时，得到耐盐雾聚天门冬氨酸酯；
得到的耐盐雾聚天门冬氨酸酯的仲胺基当量为263.5，粘度为1800mPa·s(25℃)。
实施例2
取1L的四口烧瓶，加入F520聚天门冬氨酸酯582g(1mol)，LITE-2020腰果酚树脂68.8g(0.2mol)，二丁基氧化锡0.74g(0.003mol)，然后搅拌
升温至120℃，在相对真空度为-0.095MPa下减压蒸馏反应3小时，得到耐盐雾聚天门冬氨酸酯；
得到的耐盐雾聚天门冬氨酸酯的仲胺基当量为321，粘度为3350mPa·s(25℃)。
实施例3
取1L的四口烧瓶，加入F530聚天门冬氨酸酯514g(1mol)，NX-2024腰果酚树脂75.5g(0.25mol)，钛酸四异丙酯0.58g(0.002mol)，然后搅拌升温至100℃，在相对真空度为-0.095MPa下减压蒸馏反应5小时，得到耐盐雾聚天门冬氨酸酯；
得到的耐盐雾聚天门冬氨酸酯的仲胺基当量为309，粘度为3200mPa·s(25℃)。
实施例4
取1L的四口烧瓶，加入F524聚天门冬氨酸酯666g(1mol)，NX-2020腰果酚树脂103.2g(0.3mol)，钛酸四异丙酯0.9g(0.003mol)，然后搅拌升温至125℃，在相对真空度为-0.095MPa下减压蒸馏反应4小时，得到耐盐雾聚天门冬氨酸酯；
得到的耐盐雾聚天门冬氨酸酯的仲胺基当量为350，粘度为4100mPa·s(25℃)。
对比例
对比例1
F420聚天门冬氨酸酯(深圳飞扬骏研新材料股份有限公司)，其仲胺基当量为277，粘度为1000mPa·s(25℃)。
对比例2
F520聚天门冬氨酸酯(深圳飞扬骏研新材料股份有限公司)，其仲胺基当量为291，粘度为1300mPa·s(25℃)。
对比例3
与实施例2的区别在于，LITE-2020腰果酚树脂的添加量为22.9g(0.06mol)。
对比例4
与实施例2的区别在于，LITE-2020腰果酚树脂的添加量为133.5g(0.35mol)。
表1：实施例1-4和对比例1-4中的聚天门冬氨酸酯的粘度
采用实施例1-4及对比例1-4制得的聚天门冬氨酸酯按以下重量份数的配比制成聚天门冬氨酸酯涂料，具体配比如表2：
表2：聚天门冬氨酸酯涂料配比
其中，分散剂为德国毕克的DISPERBYK-163，防沉剂为德国瓦克的气相二氧化硅消泡剂为德国毕克的BYK-1790，流平剂为德国巴斯夫的EFKA-3600，硫酸钡粒级为2200目，钛白粉为宁波新福的NTR606，硫酸锌为西班牙纽碧莱的Nubirox-213，异氰酸酯固化剂为万华化学的HT-100(HDI三聚体，异氰酸根(—NCO)的质量分数为21.7％)。
聚天门冬氨酸酯涂料的制备方法如下：
将聚天门冬氨酸酯树脂、分散剂、防沉剂、硫酸钡、磷酸锌、钛白粉投入反应釜中，控制转速为3000rpm，高速分散30分钟至涂料研磨细度低于30um，然后加入消泡剂、流平剂、醋酸丁酯，调整转速为1000rpm，搅拌10分钟得到A组分，接着取A组分与B组分的重量比按仲胺基当量：异氰酸酯基当量＝1：1.05混合，搅拌均匀后得到聚天门冬氨酸酯涂料。
性能检测试验
对上述采用实施例1-4和对比例1-4中的聚天门冬氨酸酯制得的聚天门冬氨酸酯涂料进行以下性能测试：
适用期：检测方法参照GB/T31416-2015；
实干时间：检测方法参照GB/T1728-1989；
附着力：检测方法参照GB/T9286-1998；
硬度：检测方法参照GB/T6739-2006；
耐盐雾性能：检测方法参照GB/T1771-2007。
测试数据见表3：
表3：实施例1-4和对比例1-4中聚天门冬氨酸酯制得的涂料性能数据
结合实施例1-4、对比例1-2表3的数据可以看出，采用腰果酚树脂对聚天门冬氨酸酯进行改性有利于提高其耐盐雾性能。随着腰果酚树脂添加量的增加，制得的聚天门冬氨酸酯涂料的耐盐雾性能整体呈提升趋势，其中，实施例2制得的聚天门冬氨酸酯涂料实干时间过长，对于施工有一定的影响，实施例4制得的聚天门冬氨酸酯涂料的耐盐雾性能虽然更优，但是其硬度有所下降，综合适用期、实干时间、硬度及耐盐雾性能的考虑，以实施例3的配比制得的聚天门冬氨酸酯对于涂料性能的提升更优。
结合实施例1-4、对比例3-4及表3的数据可以看出，当腰果酚树脂与聚天门冬氨酸酯的摩尔比小于0.1：1时，制得的聚天门冬氨酸酯树脂涂料
的耐盐雾提升不明显。而当腰果酚树脂与聚天门冬氨酸酯的摩尔比大于0.3：1时，制得的聚天门冬氨酸酯涂料的硬度会大大降低，达不到应用标准，并且涂料的耐盐雾性能反而降低，原因是腰果酚树脂添加量太多，支链太长，聚天门冬氨酸酯后续应用时与固化剂的交联密度会降低，导致涂料的耐盐雾效果会下降。
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。
Claims (6)
- 一种耐盐雾聚天门冬氨酸酯的制备方法，其特征在于，包括以下步骤：将聚天门冬氨酸酯、腰果酚树脂及催化剂混合于一起进行酯交换反应，控制温度为100～130℃，控制相对真空度为-0.095～-0.1MPa，搅拌反应2～5小时得到耐盐雾聚天门冬氨酸酯；其中，所述聚天门冬氨酸酯、腰果酚树脂及催化剂的摩尔比为聚天门冬氨酸酯：腰果酚树脂：催化剂＝1：0.1～0.3：0.001～0.003，所述催化剂为钛酸四异丙酯或二丁基氧化锡；所述腰果酚树脂的结构式为：
- 根据权利要求1所述的耐盐雾聚天门冬氨酸酯的制备方法，其特征在于：所述聚天门冬氨酸酯为F420、F520、F530、F540、F2850、F524中的一种或多种的组合。
- 一种耐盐雾聚天门冬氨酸酯，其特征在于：由权利要求1-2中任一项所述的耐盐雾聚天门冬氨酸酯的制备方法制得。
- 一种耐盐雾聚天门冬氨酸酯涂料，其特征在于：所述聚天门冬氨酸酯涂料由A组分和B组分两种组分在室温下混合固化成型，所述A组分至少包括权利要求3所述的耐盐雾聚天门冬氨酸酯，所述B组分为异氰酸酯固化剂。
- 根据权利要求4所述的耐盐雾聚天门冬氨酸酯涂料，其特征在于：所述A组分还包括分散剂、防沉剂、消泡剂、硫酸钡、钛白粉、磷酸锌、流平剂、醋酸丁酯中的一种或多种。
- 根据权利要求4或5所述的耐盐雾聚天门冬氨酸酯涂料，其特征在于：所述A组分与B组分的质量比按A组分中仲胺基当量：B组分中异氰酸酯基当量＝1：1.05计。
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