CN116179021A - Water-resistant salt-fog-resistant water-based universal paint color paste and application thereof - Google Patents
Water-resistant salt-fog-resistant water-based universal paint color paste and application thereof Download PDFInfo
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- CN116179021A CN116179021A CN202310050193.0A CN202310050193A CN116179021A CN 116179021 A CN116179021 A CN 116179021A CN 202310050193 A CN202310050193 A CN 202310050193A CN 116179021 A CN116179021 A CN 116179021A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003973 paint Substances 0.000 title claims abstract description 68
- 239000003822 epoxy resin Substances 0.000 claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 62
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 239000007921 spray Substances 0.000 claims abstract description 23
- 239000000049 pigment Substances 0.000 claims abstract description 22
- 238000005303 weighing Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000007873 sieving Methods 0.000 claims abstract description 11
- 238000010298 pulverizing process Methods 0.000 claims abstract description 7
- 239000006184 cosolvent Substances 0.000 claims abstract description 5
- 239000002562 thickening agent Substances 0.000 claims abstract description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 45
- 229960000892 attapulgite Drugs 0.000 claims description 43
- 229910052625 palygorskite Inorganic materials 0.000 claims description 43
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003651 drinking water Substances 0.000 claims description 15
- 235000020188 drinking water Nutrition 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 10
- QQVKNEQDEIZBLC-UHFFFAOYSA-N hepta-2,6-dienoic acid Chemical compound OC(=O)C=CCCC=C QQVKNEQDEIZBLC-UHFFFAOYSA-N 0.000 claims description 10
- CPVUNKGURQKKKX-BQYQJAHWSA-N trans-dec-3-enoic acid Chemical compound CCCCCC\C=C\CC(O)=O CPVUNKGURQKKKX-BQYQJAHWSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical group CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004566 building material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 21
- 239000012065 filter cake Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- -1 carboxylic acid amine salt Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011011 black crystal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle 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
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses water-resistant salt spray-resistant water-based universal paint color paste and application thereof, and belongs to the technical field of paint color paste. The invention is used for solving the technical problems that the drying time of a water-based paint color paste paint film is longer, the salt spray resistance and the waterproof performance of the water-based paint color paste paint film are to be further improved, and the water-based salt spray resistance water-based universal paint color paste, and the preparation method of the water-based salt spray resistance water-based universal paint color paste comprises the following operation steps: weighing 12-16 parts of rust-proof pigment according to parts by weight, adding into a pulverizer for pulverization, and sieving with a 300-mesh sieve for later use; according to the weight portions, 35 to 40 portions of modified epoxy resin, 35 to 40 portions of water, 12 to 16 portions of crushed antirust pigment, 8 to 12 portions of cosolvent and 3 to 5 portions of thickener are weighed. The invention not only effectively improves the flexibility of the water-based paint color paste paint film and shortens the drying time, but also effectively improves the salt spray resistance and the water resistance of the water-based paint color paste paint film.
Description
Technical Field
The invention relates to the technical field of paint color paste, in particular to water-based universal paint color paste resistant to water and salt mist and application thereof.
Background
The corrosion of metals can cause huge damage to machinery, equipment, bridges and the like, and in order to reduce economic loss caused by corrosion, anticorrosive paint is generally coated on the metal surface. Along with the implementation of national environmental protection laws, environmental protection policies are more and more stringent, along with the increasingly strict environmental protection control of chemical enterprises, the development of the coating industry is borrowed, and the water-based coating color paste gradually replaces solvent-based coating color paste to become a development trend. However, the comprehensive capability of the water-based general paint color paste in the prior art can not reach the technical standard of the solvent-based paint color paste.
In the preparation process of the water-based general paint color paste in the prior art, epoxy resin is generally selected as a film forming material base material and antirust pigment to prepare a paint, and bisphenol A type epoxy resin is taken as an example, and the bisphenol A type epoxy resin has excellent chemical resistance and adhesive force due to the fact that the bisphenol A type epoxy resin paint color paste contains benzene rings and ether bonds in a molecular structure, but a paint film prepared from the bisphenol A type epoxy resin paint color paste is poor in flexibility and long in drying time, the antirust pigment is generally an inorganic material, the dispersion stability of the antirust pigment in the paint color paste needs to be further improved, and the risk that external water molecules, oxygen or corrosive media permeate the paint film is large due to uneven dispersion of the antirust pigment, so that the salt fog resistance and the waterproof performance of the paint film need to be further improved.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide water-resistant and salt-fog-resistant water-based universal paint color paste and application thereof, which are used for solving the technical problems that in the prior art, paint color paste made of bisphenol A epoxy resin needs longer time for drying a paint film, rust-resistant pigment is unevenly dispersed in the paint color paste, external water molecules, oxygen or corrosive medium penetrate the paint film at a higher risk, and salt fog resistance and water resistance of the paint film are required to be further improved.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the water-resistant salt spray-resistant water-based universal paint color paste comprises the following operation steps:
s1, weighing 12-16 parts of rust-proof pigment according to parts by weight, adding into a pulverizer for pulverization, and sieving with a 300-mesh sieve for later use;
s2, weighing 35-40 parts of modified epoxy resin, 35-40 parts of water, 12-16 parts of crushed antirust pigment, 8-12 parts of cosolvent, 3-5 parts of thickener, 1-1.5 parts of cross-linking agent and 0.8-1.2 parts of dispersing agent according to parts by weight, adding into a container, stirring, and dispersing for 10-15min at a stirring speed of 550-600r/min to obtain mixed dispersion;
s3, adding 0.3-0.5 part by weight of defoaming agent into the mixed dispersion liquid, stirring at the stirring speed of 300-400r/min for 3-5min, and passing through a 200-mesh filter screen to obtain the water-resistant salt mist-resistant water-based universal coating color paste.
Further, the antirust pigment is formed by mixing iron oxide black and composite ferrotitanium powder according to a weight ratio of 3:2, wherein the cosolvent is dipropylene glycol butyl ether or propylene glycol diethyl ether, the thickener is modified attapulgite, the cross-linking agent is polycarbodiimide, the dispersing agent is Silco Sperse Hld-5, and the defoamer is any one of GPE10, GPE20, GPE30 and GPE40.
Further, the preparation method of the modified epoxy resin comprises the following operation steps:
a1, adding n-butanol, epoxy resin and ethylene glycol monobutyl ether into a three-neck flask, raising the temperature of the three-neck flask to 105-115 ℃, and stirring until the epoxy resin is completely dissolved;
a2, sequentially adding n-butanol, trans-3-decenoic acid and an initiator into the flask, and stirring for 10-20min to obtain a dripping solution for later use;
a3, dropwise adding the dropwise adding liquid into the three-neck flask by using a constant-pressure dropping funnel, finishing the dropwise adding after 80-100min, preserving the heat and reacting for 4-6h, finishing the reaction, and performing post-treatment to obtain an intermediate I;
the principle of the synthesis reaction of the intermediate I is as follows:
and A4, sequentially adding n-butanol, an intermediate I, 2, 6-heptadienoic acid and a catalyst into a three-neck flask, introducing nitrogen into the three-neck flask, stirring, raising the temperature of the three-neck flask to 110-118 ℃, reacting for 6-8h, detecting an acid value lower than 5, and performing post treatment to obtain the modified epoxy resin.
The synthetic reaction principle of the modified epoxy resin is as follows:
further, the weight ratio of n-butanol, epoxy resin and ethylene glycol monobutyl ether in the step A1 is 5:3:1, and the weight ratio of n-butanol, trans-3-decenoic acid, initiator and epoxy resin in the step A2 is as follows: 3:1:0.2:3.
Further, the initiator in the step A2 is any one of dibenzoyl peroxide and azodiisobutyronitrile, the epoxy resin is bisphenol A type epoxy resin, and the model is E-51 or E-55.
Further, the post-processing operation in the step A3 includes: after the reaction is completed, the temperature of the three-neck flask is increased to 110-120 ℃, the pressure is reduced, distillation is carried out until no liquid flows out, the temperature of the three-neck flask is reduced to room temperature, drinking water and 5-amino-1-pentanol are added into the three-neck flask, stirring is carried out for 40-50min, standing is carried out, liquid separation is carried out, oily matters on the top layer are removed, the water phase is added into a rotary evaporator, the temperature is 70-80 ℃ and reduced, distillation is carried out until no liquid flows out, an intermediate I is obtained, wherein the molar ratio of the 5-amino-1-pentanol to the trans-3-decenoic acid is 1:0.9, and the consumption of the drinking water is 1.2 times the weight of the n-butanol in the step A2.
Further, in the step A4, the weight ratio of the n-butanol, the intermediate I, the 2, 6-heptadienoic acid and the catalyst is 5:2:0.8:0.05, wherein the catalyst is tetrabutylammonium bromide.
Further, the post-processing operation in the step A4 includes: and after the reaction is completed, maintaining the temperature of the three-neck flask at 110-118 ℃, and carrying out reduced pressure distillation until no liquid flows out, thereby obtaining the modified epoxy resin.
Further, the preparation of the modified attapulgite comprises the following operation steps:
weighing 10 parts of attapulgite and 25 parts of 0.5mol/L hydrochloric acid aqueous solution according to parts by weight, adding into a beaker, stirring for 20min, soaking for 3-5h, filtering, placing a filter cake into a drying oven with the temperature of 80 ℃, and drying to constant weight to obtain acidified attapulgite;
adding the acidified attapulgite into a muffle furnace at 600 ℃, roasting for 2.5-3.5 hours, and crushing the muffle furnace until the temperature reaches room temperature to obtain the roasted attapulgite;
and B3, weighing 10 parts of baked attapulgite and 20 parts of drinking water according to parts by weight, adding into a beaker, stirring for 30-50min, carrying out suction filtration, leaching a filter cake to the center by using the drinking water, placing the filter cake into a baking oven with the temperature of 70-80 ℃, drying for 10-12h, and sieving with a 300-mesh screen to obtain the modified attapulgite.
The application of the water-resistant salt spray-resistant water-based universal paint color paste applies the water-resistant salt spray-resistant water-based universal paint color paste to the antirust primer of the hardware building material.
The invention has the following beneficial effects:
1. the water-resistant salt spray-resistant water-based universal paint color paste takes bisphenol A type epoxy resin as a basic raw material, and the bisphenol A type epoxy resin has good corrosion resistance, so that the prepared paint color paste has excellent corrosion resistance, in the preparation process, trans-3-decenoic acid generates a trans-3-decenoic acid copolymer through free radical reaction, and the trans-3-decenoic acid copolymer is polycondensed with alpha-H on the ether bond clinical carbon of the bisphenol A type epoxy resin under the action of an initiator, the trans-3-decenoic acid copolymer is grafted on the bisphenol A type epoxy resin, and in the post-treatment process, carboxyl on the trans-3-decenoic acid copolymer reacts with amino of 5-amino-1-pentanol to generate carboxylic acid amine salt, the pH of the intermediate I is reduced, the hydrophilic performance of the amine carboxylate and the hydroxyl is greatly improved, the dispersion stability of the bisphenol A epoxy resin in water environment is improved, epoxy groups at two ends of the intermediate I are opened under the action of a catalyst and are in butt joint with carboxyl groups on 2, 6-heptadienoic acid, the whole chain length of the modified epoxy resin is increased, the flexibility and the adhesiveness of the modified epoxy resin are improved, the adhesive force of a paint film is improved, and the 2, 6-heptadienoic acid grafted at two ends of the modified epoxy resin contains a large number of unsaturated double bonds which can be oxidized and polymerized under the condition of existence of room temperature oxygen, so that the drying time of the paint film is shortened.
2. According to the water-resistant salt spray-resistant water-based universal coating color paste, after the attapulgite is soaked with acid, partial structures in the attapulgite are dissolved to form pores, the specific surface area of the attapulgite is increased, and then crystal water in the attapulgite is removed through high-temperature roasting, so that the internal structure of the attapulgite is loosened, the attapulgite can be stably dispersed in the coating color paste, iron oxide black and composite iron titanium powder are used as rust-proof pigments, powder with the particle size of 8 mu m or more is formed after the powder is crushed and passes through a 300-mesh screen, holes on the modified attapulgite can absorb the powder, the dispersion stability of the powder in the coating color paste is improved, bubbles existing in a coating color paste system are avoided due to the existence of the bubbles in a stirring process by using a defoaming agent, the small-size effect is achieved, the paint film is effectively improved in the property, the risk that water molecules, oxygen or corrosive mediums permeate the paint film is greatly reduced, the salt spray resistance and the waterproof performance of the paint film are improved, and the physical structure of ferroferric oxide black crystal is stable, and the rust-resistant performance is excellent.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of water-resistant and salt-fog-resistant water-based universal paint color paste, which comprises the following operation steps:
preparing modified epoxy resin:
weighing 500g of n-butanol, 300g of epoxy resin and 100g of ethylene glycol monobutyl ether according to parts by weight, adding into a three-neck flask, heating the three-neck flask to 105 ℃, and stirring until the epoxy resin is completely dissolved, wherein the epoxy resin is bisphenol A type epoxy resin with the model of E-51;
weighing 300g of n-butanol, 100g of trans-3-decenoic acid and 20g of dibenzoyl peroxide according to parts by weight, adding into a beaker, stirring for 10min, and uniformly mixing the systems to obtain a dripping solution;
dropwise adding dropwise added liquid into a three-neck flask by using a constant-pressure dropping funnel, completing dropwise adding for 80min, preserving heat, reacting for 4h, finishing the reaction, raising the temperature of the three-neck flask to 110 ℃, carrying out reduced pressure distillation until no liquid flows out, reducing the temperature of the three-neck flask to room temperature, adding 600g of drinking water and 67.5g of 5-amino-1-amyl alcohol into the three-neck flask, stirring for 40min, standing, separating liquid, removing oily matters on the top layer, adding the water phase into a rotary evaporator, carrying out reduced pressure distillation at 70 ℃ until no liquid flows out, and obtaining an intermediate I;
500g of n-butanol, 200g of intermediate I, 80g of 2, 6-heptadienoic acid and 5g of tetrabutylammonium bromide are sequentially added into a three-neck flask, nitrogen is introduced into the three-neck flask, the temperature of the three-neck flask is increased to 110 ℃, the reaction is carried out for 6 hours, the acid value is detected to be lower than 5, the reaction is completed, the temperature of the three-neck flask is kept at 110 ℃, and the three-neck flask is distilled under reduced pressure until no liquid flows out, so that the modified epoxy resin is obtained.
Preparing modified attapulgite:
weighing 50g of attapulgite and 125g of 0.5mol/L hydrochloric acid aqueous solution according to parts by weight, adding into a beaker, stirring for 20min, soaking for 3h, filtering, placing a filter cake into a drying box with the temperature of 80 ℃, and drying to constant weight to obtain acidified attapulgite;
adding the acidified attapulgite into a muffle furnace, roasting for 2.5 hours at 600 ℃, and crushing the attapulgite until the temperature reaches the room temperature to obtain roasted attapulgite;
weighing 50g of baked attapulgite and 100 parts of drinking water according to parts by weight, adding into a beaker, stirring for 30min, carrying out suction filtration, leaching a filter cake to the center by using the drinking water, placing the filter cake into a baking oven with the temperature of 70 ℃, drying for 10h, and sieving with a 300-mesh screen to obtain the modified attapulgite.
Preparing paint color paste:
weighing 72g of iron oxide black and 48g of composite ferrotitanium powder according to parts by weight, adding into a pulverizer for pulverization, and sieving with a 300-mesh sieve to obtain a pulverized antirust pigment;
weighing 350g of modified epoxy resin, 350g of water, 120g of crushed antirust pigment, 80g of dipropylene glycol butyl ether, 30g of modified attapulgite, 10g of polycarbodiimide and 8g of Silco Sperse Hld-5 according to parts by weight, adding into a container, stirring at a stirring speed of 550r/min, and dispersing for 10min to obtain a mixed dispersion;
3g of defoaming agent is added into the mixed dispersion liquid for stirring, the stirring speed is 300r/min, the stirring is carried out for 3min, and the mixture passes through a 200-mesh filter screen to obtain the water-resistant salt-fog-resistant water-based universal coating color paste, wherein the type of the defoaming agent is GPE10.
Example 2
The embodiment provides a preparation method of water-resistant and salt-fog-resistant water-based universal paint color paste, which comprises the following operation steps:
preparing modified epoxy resin:
weighing 500g of n-butanol, 300g of epoxy resin and 100g of ethylene glycol monobutyl ether according to parts by weight, adding into a three-neck flask, heating the three-neck flask to 105-115 ℃, and stirring until the epoxy resin is completely dissolved, wherein the epoxy resin is bisphenol A type epoxy resin with the model of E-51;
300g of n-butanol, 100g of trans-3-decenoic acid and 20g of initiator are weighed according to parts by weight, added into a beaker, stirred for 15min, and the system is uniformly mixed to obtain a dripping liquid;
dropwise adding dropwise added liquid into a three-neck flask by using a constant-pressure dropping funnel, dropwise adding for 90min, carrying out heat preservation reaction for 5h, finishing the reaction, raising the temperature of the three-neck flask to 115 ℃, carrying out reduced pressure distillation until no liquid flows out, reducing the temperature of the three-neck flask to room temperature, adding 600g of drinking water and 67.5g of 5-amino-1-amyl alcohol into the three-neck flask, stirring for 45min, standing, separating liquid, removing oily matters on the top layer, adding the water phase into a rotary evaporator, carrying out reduced pressure distillation at the temperature of 75 ℃ until no liquid flows out, and obtaining an intermediate I;
500g of n-butanol, 200g of intermediate I, 80g of 2, 6-heptadienoic acid and 5g of tetrabutylammonium bromide are sequentially added into a three-neck flask, nitrogen is introduced into the three-neck flask, the temperature of the three-neck flask is increased to 114 ℃ and is reacted for 7 hours, the acid value is detected to be lower than 5, the reaction is completed, the temperature of the three-neck flask is kept at 114 ℃, and the three-neck flask is distilled under reduced pressure until no liquid flows out, so that the modified epoxy resin is obtained.
Preparing modified attapulgite:
weighing 50g of attapulgite and 125g of 0.5mol/L hydrochloric acid aqueous solution according to parts by weight, adding into a beaker, stirring for 20min, soaking for 4h, filtering, placing a filter cake into a drying box with the temperature of 80 ℃, and drying to constant weight to obtain acidified attapulgite;
adding the acidified attapulgite into a muffle furnace, roasting for 3 hours at 600 ℃, and crushing the muffle furnace until the temperature reaches the room temperature to obtain the roasted attapulgite;
weighing 50g of baked attapulgite and 100g of drinking water according to parts by weight, adding into a beaker, stirring for 40min, carrying out suction filtration, leaching a filter cake to the center by using the drinking water, placing the filter cake into a baking oven with the temperature of 75 ℃, drying for 11h, and sieving with a 300-mesh screen to obtain the modified attapulgite.
Preparing paint color paste:
weighing 84g of iron oxide black and 56g of composite iron titanium powder according to parts by weight, adding into a pulverizer for pulverization, and sieving with a 300-mesh sieve to obtain a pulverized antirust pigment;
weighing 375g of modified epoxy resin, 375g of water, 140g of crushed antirust pigment, 100g of propylene glycol diethyl ether, 40g of modified attapulgite, 12.5g of polycarbodiimide and 5-10 g of Silco Sperse Hld-5 according to parts by weight, adding into a container, stirring at 575r/min, and dispersing for 13min to obtain a mixed dispersion;
adding 4g of defoaming agent into the mixed dispersion liquid, stirring at the stirring speed of 300-400r/min, stirring for 3-5min, and passing through a 200-mesh filter screen to obtain the water-resistant salt spray-resistant water-based universal coating color paste, wherein the type of the defoaming agent is GPE20.
Example 3
The embodiment provides a preparation method of water-resistant and salt-fog-resistant water-based universal paint color paste, which comprises the following operation steps:
preparing modified epoxy resin:
weighing 500g of n-butanol, 300g of epoxy resin and 100g of ethylene glycol monobutyl ether according to parts by weight, adding into a three-neck flask, heating the three-neck flask to 115 ℃, and stirring until the epoxy resin is completely dissolved, wherein the epoxy resin is bisphenol A type epoxy resin with the model of E-55;
300g of n-butanol, 100g of trans-3-decenoic acid and 20g of initiator are weighed according to parts by weight, added into a beaker, stirred for 20min, and the system is uniformly mixed to obtain a dripping liquid;
dropwise adding dropwise added liquid into a three-neck flask by using a constant-pressure dropping funnel, completing dropwise adding for 100min, preserving heat, reacting for 6h, finishing the reaction, raising the temperature of the three-neck flask to 120 ℃, carrying out reduced pressure distillation until no liquid flows out, reducing the temperature of the three-neck flask to room temperature, adding 600g of drinking water and 67.5g of 5-amino-1-amyl alcohol into the three-neck flask, stirring for 50min, standing, separating liquid, removing oily matters on the top layer, adding the water phase into a rotary evaporator, carrying out reduced pressure distillation at the temperature of 80 ℃ until no liquid flows out, and obtaining an intermediate I;
500g of n-butanol, 200g of intermediate I, 80g of 2, 6-heptadienoic acid and 5g of tetrabutylammonium bromide are sequentially added into a three-neck flask, nitrogen is introduced into the three-neck flask, the temperature of the three-neck flask is increased to 118 ℃ and is reacted for 8 hours, the acid value is detected to be lower than 5, the reaction is completed, the temperature of the three-neck flask is kept at 118 ℃, and the three-neck flask is distilled under reduced pressure until no liquid flows out, so that the modified epoxy resin is obtained.
Preparing modified attapulgite:
weighing 50g of attapulgite and 125g of 0.5mol/L hydrochloric acid aqueous solution according to parts by weight, adding into a beaker, stirring for 20min, soaking for 5h, filtering, placing a filter cake into a drying box with the temperature of 80 ℃, and drying to constant weight to obtain acidified attapulgite;
adding the acidified attapulgite into a muffle furnace, roasting for 3.5 hours at 600 ℃, and crushing the attapulgite until the temperature reaches the room temperature to obtain roasted attapulgite;
weighing 50g of baked attapulgite and 100g of drinking water according to parts by weight, adding into a beaker, stirring for 50min, carrying out suction filtration, leaching a filter cake to the center by using the drinking water, placing the filter cake into an oven with the temperature of 80 ℃, drying for 12h, and sieving with a 300-mesh screen to obtain the modified attapulgite.
Preparing paint color paste:
weighing 96g of iron oxide black and 64g of composite ferrotitanium powder according to parts by weight, adding into a pulverizer for pulverization, and sieving with a 300-mesh sieve to obtain a pulverized antirust pigment;
400g of modified epoxy resin, 400g of water, 160g of crushed antirust pigment, 120g of dipropylene glycol butyl ether, 50g of modified attapulgite, 15g of polycarbodiimide and 12g of Silco Sperse Hld-5 are weighed according to parts by weight, added into a container and stirred, the stirring speed is 600r/min, and dispersed for 15min, so as to obtain mixed dispersion;
and adding 5g of defoaming agent into the mixed dispersion liquid, stirring for 5min at the stirring speed of 400r/min, and filtering with a 200-mesh filter screen to obtain the water-resistant salt-fog-resistant water-based universal coating color paste, wherein the type of the defoaming agent is GPE40.
Comparative example 1
The comparative example differs from example 3 in that the epoxy resin was not modified.
Comparative example 2
The comparative example differs from example 3 in that the intermediate I obtained by modification of the epoxy-modified resin was used directly as the modified epoxy resin.
Comparative example 3
The comparative example differs from example 3 in that the rust inhibitive pigment and the modified attapulgite clay were passed through a 100 mesh screen after pulverization, and the sieving operation in the preparation of the paint color paste was eliminated.
Performance test:
the paint colors prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to water stirring to dilute the paint colors to a construction viscosity, and then coated on an experimental material, and the adhesion, water resistance and neutral salt spray resistance and drying time of the paint film were tested, wherein the adhesion of the paint film was tested with reference to the standard GB/T5210-2006 "paint and varnish pull-off adhesion test", and the water resistance was tested with reference to the standard GB/T1733-1993 "paint film Water resistance assay" method A: the immersion test method is used for testing, the neutral salt spray resistance is referred to standard GB/T1771-2007 for testing neutral salt spray resistance of paint and varnish, the salt spray resistance duration of a paint film is detected, the drying time is referred to standard GB/T1728-2020 for testing paint film and putty film drying time measuring method, and specific performance testing results are shown in the following table:
from the analysis of the performance test data in the above table, it is known that:
according to the water-resistant salt spray-resistant water-based universal coating color paste, the bisphenol A type epoxy resin is modified, the trans-3-decenoic acid copolymer is grafted on the bisphenol A type epoxy resin, and the carboxyl on the trans-3-decenoic acid copolymer is neutralized to form the ammonium carboxylate salt, and then the 2, 6-heptadienoic acid is grafted at two ends of the bisphenol A type epoxy resin, so that the modified epoxy resin is obtained, the adhesive force of the coating color paste is effectively increased, the drying time of a paint film with the coating color paste is shortened, the compactness of the paint film is effectively improved due to the small volume effect of the pigment color paste, and the risk that water molecules, oxygen or corrosive media penetrate the paint film is greatly reduced, so that the salt spray resistance and the waterproof performance of the paint film are improved.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (9)
1. The preparation method of the water-resistant salt spray-resistant water-based universal paint color paste is characterized by comprising the following operation steps of:
s1, weighing 12-16 parts of rust-proof pigment according to parts by weight, adding into a pulverizer for pulverization, and sieving with a 300-mesh sieve for later use;
s2, weighing 35-40 parts of modified epoxy resin, 35-40 parts of water, 12-16 parts of crushed antirust pigment, 8-12 parts of cosolvent, 3-5 parts of thickener, 1-1.5 parts of cross-linking agent and 0.8-1.2 parts of dispersing agent according to parts by weight, adding into a container, stirring, and dispersing for 10-15min at a stirring speed of 550-600r/min to obtain mixed dispersion;
s3, adding 0.3-0.5 part by weight of defoaming agent into the mixed dispersion liquid, stirring at the stirring speed of 300-400r/min for 3-5min, and passing through a 200-mesh filter screen to obtain the water-resistant salt mist-resistant water-based universal coating color paste.
2. The water-resistant salt spray-resistant water-based universal paint color paste according to claim 1, wherein the rust-resistant pigment is formed by mixing iron oxide black and composite iron titanium powder according to a weight ratio of 3:2, the cosolvent is dipropylene glycol butyl ether or propylene glycol diethyl ether, the thickener is modified attapulgite, the crosslinking agent is polycarbodiimide, the dispersing agent is Silco Sperse Hld-5, and the defoaming agent is any one of GPE10, GPE20, GPE30 and GPE40.
3. The water-resistant salt spray-resistant aqueous universal coating color paste according to claim 1, wherein the preparation method of the modified epoxy resin comprises the following operation steps:
a1, adding n-butanol, epoxy resin and ethylene glycol monobutyl ether into a three-neck flask, raising the temperature of the three-neck flask to 105-115 ℃, and stirring until the epoxy resin is completely dissolved;
a2, sequentially adding n-butanol, trans-3-decenoic acid and an initiator into the flask, and stirring for 10-20min to obtain a dripping solution for later use;
a3, dropwise adding the dropwise adding liquid into the three-neck flask by using a constant-pressure dropping funnel, finishing the dropwise adding after 80-100min, preserving the heat and reacting for 4-6h, finishing the reaction, and performing post-treatment to obtain an intermediate I;
and A4, sequentially adding n-butanol, an intermediate I, 2, 6-heptadienoic acid and a catalyst into a three-neck flask, introducing nitrogen into the three-neck flask, stirring, raising the temperature of the three-neck flask to 110-118 ℃, reacting for 6-8h, detecting an acid value lower than 5, and performing post treatment to obtain the modified epoxy resin.
4. The water-resistant and salt-fog-resistant aqueous universal paint color paste according to claim 3, wherein the weight ratio of n-butanol, epoxy resin and ethylene glycol monobutyl ether in the step A1 is 5:3:1, and the weight ratio of n-butanol, trans-3-decenoic acid, initiator and epoxy resin in the step A2 is as follows: 3:1:0.2:3.
5. The water-resistant and salt-fog-resistant aqueous universal coating color paste according to claim 3, wherein the initiator in the step A2 is any one of dibenzoyl peroxide and azodiisobutyronitrile, the epoxy resin is bisphenol A type epoxy resin, and the type of the epoxy resin is E-51 or E-55.
6. The water-resistant and salt spray-resistant aqueous universal coating color paste according to claim 3, wherein the post-treatment operation in step A3 comprises: after the reaction is completed, the temperature of the three-neck flask is increased to 110-120 ℃, the pressure is reduced, distillation is carried out until no liquid flows out, the temperature of the three-neck flask is reduced to room temperature, drinking water and 5-amino-1-pentanol are added into the three-neck flask, stirring is carried out for 40-50min, standing is carried out, liquid separation is carried out, oily matters on the top layer are removed, the water phase is added into a rotary evaporator, the temperature is 70-80 ℃ and reduced, distillation is carried out until no liquid flows out, an intermediate I is obtained, wherein the molar ratio of the 5-amino-1-pentanol to the trans-3-decenoic acid is 1:0.9, and the consumption of the drinking water is 1.2 times the weight of the n-butanol in the step A2.
7. The water-resistant and salt-fog-resistant aqueous universal coating color paste according to claim 3, wherein in the step A4, the weight ratio of n-butanol, an intermediate I, 2, 6-heptadienoic acid and a catalyst is 5:2:0.8:0.05, and the catalyst is tetrabutylammonium bromide.
8. The water-resistant and salt spray-resistant aqueous universal coating color paste according to claim 3, wherein the post-treatment operation in step S4 comprises: and after the reaction is completed, maintaining the temperature of the three-neck flask at 110-118 ℃, and carrying out reduced pressure distillation until no liquid flows out, thereby obtaining the modified epoxy resin.
9. The application of the water-resistant salt-fog-resistant water-based universal paint color paste is characterized in that the water-resistant salt-fog-resistant water-based universal paint color paste as claimed in any one of claims 1 to 8 is applied to antirust primer of hardware building materials.
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