CN110527414B - Slow-speed polyurea primer-topcoat coating and preparation method thereof - Google Patents
Slow-speed polyurea primer-topcoat coating and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The slow polyurea primer-topcoat coating is prepared by mixing a base material, a curing agent and a diluent; the base material consists of polyaspartic acid ester resin, trimethylated melamine formaldehyde resin, cardanol phenolic aldehyde amine, pigment, filler, auxiliary agent and solvent. The invention also discloses a preparation method of the slow polyurea primer-topcoat coating. The working life of the coating construction is more than or equal to 4 hours, and the surface drying time is 35-60 min; the product is sprayed on the surface of a metal or concrete substrate, and a coating film with high drying speed and excellent weather resistance and salt spray resistance can be formed.
Description
Technical Field
The invention relates to a coating and a preparation method thereof, in particular to a slow polyurea primer-topcoat coating and a preparation method thereof.
Background
The polyaspartic ester is prepared by Michael addition reaction of dialkyl maleate (or dialkyl fumarate) and aliphatic diamine, primary amine is converted into secondary amine, the reaction activity of hydrogen atoms and isocyanic acid radicals is reduced, and simultaneously the reaction speed is greatly reduced due to steric effect.
Polyaspartate resins were originally used as reactive diluents for solvent borne polyurethane coatings and were capable of being blended with hydroxyl-containing polyesters, acrylate copolymers, and reducing the VOC content of the coating system. In the early nineties of the 20 th century, two-component aliphatic polyurea products were commercialized. In traditional polyurea technology, the gel time ranges from a few seconds to a few minutes; the polyaspartate polyurea technology belongs to the slow drying category for common polyurea, and the curing time is as long as 120 min. However, in the polyaspartate polyurea technology, the construction pot life after the base material is matched with the curing agent is still short, and is from several minutes to dozens of minutes. Materials that are formulated over the pot life are unusable and therefore the use of short pot life aspartate polyurea coatings is greatly limited.
The isocyanate component used in polyaspartate polyurea technology is an aliphatic isocyanate dimer or trimer. Thus, the weather resistance is excellent. The technology is mainly used in the construction occasion of the thin-coating finish paint which is particularly concerned about high gloss and excellent color retention, but the salt spray resistance is still not ideal, and the technology cannot be applied to the occasion of primer-topcoat coating.
CN104804633A discloses a low-temperature quick-drying acrylic polyurethane coating, which consists of a component A and a component B in a mass ratio of A to B, wherein A is 100 (20-27); the component A comprises the following components in percentage by mass: 20-45% of hydroxyl acrylic resin, 4-7% of amino resin, 2-12% of modified polyaspartic acid ester, 4-10% of pigment, 8-20% of filler, 0.1-2% of dispersing agent, 0.1-2% of defoaming agent, 0.1-2% of flatting agent, 0.1-2% of silane coupling agent, 0.1-2% of pH regulator and 15-25% of mixed solvent; the component B is isophorone diisocyanate. Hydroxyl acrylic resin, amino resin, modified polyaspartic acid ester and isophorone diisocyanate are used for crosslinking to form a film. However, the invention does not describe the specific type and example of the amino resin, and the common amino resin capable of reacting with isocyanate contains a small molecular alcohol solvent which can block the isocyanate curing agent and influence the crosslinking density. In addition, the hydroxyl acrylic resin is introduced in the method, polyurethane chain segments are formed in the crosslinking process, and pure polyurea coating is not formed, so that an additional catalyst is required to promote the crosslinking reaction of isocyanate groups and hydroxyl groups.
CN106243981A discloses a wind power blade coating with high wind and sand erosion resistance and a preparation method thereof, wherein the coating is prepared by mixing a base material and a curing agent, or further comprises a diluent; the base material comprises polyaspartic acid ester resin, polyurethane resin, pigment, a flatting agent, a defoaming agent, a scratch-proof auxiliary agent, a catalyst and a solvent; the curing agent comprises aliphatic isocyanate, polyether polyol and organic metal salt catalyst; the diluent comprises butyl acetate and a high boiling point solvent. The preparation method comprises the steps of preparing a base material, preparing a curing agent and preparing a diluent, and finally mixing the prepared base material and the curing agent or adding the diluent for mixing. The composition has excellent weather resistance, is suitable for being used as a finish, has poor salt spray resistance, and is not suitable for being used as a primer or a primer-topcoat coating.
CN105593259A discloses a coating composition comprising: a) a film-forming resin comprising secondary amine groups, b) a polyisocyanate curing agent, and c) solid particles of an amino resin based polymer. The coating comprises film-forming resin with secondary amine groups, polyisocyanate curing agent and solid particles based on amino resin polymer, and has excellent weather resistance and salt mist resistance to be improved.
CN109266157A discloses a preparation method of a waterborne polyurea modified epoxy ester resin, which comprises the following steps: the waterborne polyurea modified epoxy ester resin is formed by graft copolymerization of a polyurea modified aliphatic epoxy ester prepolymer A and a monomer mixture B; the mass ratio B/A of the monomer mixture B to the prepolymer A is 0.35-0.95; the monomer mixture B is formed by mixing various ethylenically unsaturated monomers and an initiator; the prepolymer A is formed by addition polymerization of aliphatic epoxy ester C and isocyanate-terminated polyurea D; the mass ratio D/C of the isocyanate-terminated polyurea D to the aliphatic epoxy ester C is 0.02-0.20; the aqueous polyurea modified epoxy ester resin has the advantages that the diluent is propylene glycol methyl ether acetate, and the aqueous polyurea modified epoxy ester resin still belongs to a micromolecular alcohol solvent, and can block the isocyanate curing agent to influence the crosslinking density of a coating film.
CN105462484A discloses a primer-topcoat integrated anticorrosive paint modified based on polyaspartic acid ester. The anticorrosive paint comprises, by mass, 20-35% of polyaspartic acid ester, 10-18% of modified resin, 0.2-0.8% of defoaming agent, 0.3-0.5% of flatting agent, 0.5-1.5% of ultraviolet absorber, 32-42% of pigment, 10-25% of filler, 5-10% of solvent, 20-29% of curing agent and 1-5% of flatting agent. The gloss of the coating film described is less than 90%, and the coating film cannot be applied to a case where a high gloss is required.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the slow polyurea primer-topcoat integrated coating which has long service life, excellent salt spray resistance and high gloss.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of the slow-speed polyurea primer-topcoat integrated coating, which is simple to operate and suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a slow-speed polyurea primer-topcoat coating is prepared by mixing a base material, a curing agent and a diluent; the base material consists of polyaspartic acid ester resin, trimethylated melamine formaldehyde resin, cardanol phenolic aldehyde amine, pigment, filler, auxiliary agent and solvent.
Further, the polyaspartic acid ester resin is formed by mixing a polymer A and a polymer B according to the mass ratio of 5-7: 1.
Further, the polymer A is prepared by reacting 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, maleic acid dicarballyl ester and tertiary carbonic acid glycidyl ester according to the molar ratio of 1.0: 1.75-1.95: 0.05-0.25; the polymer B is Desmophen NH1420 or F420 resin.
The dicacardanol maleate can effectively improve the salt spray resistance of a coating film, and the long-chain structure of the dicacardanol maleate improves the steric hindrance near a secondary amine structure in the polyaspartic acid ester resin, so that the construction pot life of the coating is prolonged; the branched carbon chain structure of the tertiary carbonic acid glycidyl ester can improve the weather resistance of coating and prolong the construction pot life of the coating, and the epoxy group of the tertiary carbonic acid glycidyl ester plays a role in eliminating residual primary amine and is also beneficial to prolonging the construction pot life of the coating.
Further, the solid content of the trimethyletherified melamine formaldehyde resin is 80%, and the solvent is aliphatic long-chain branched unit alcohol. The carbon chain of the aliphatic long-chain branched unit alcohol is C16-C26; the aliphatic long-chain branched unit alcohol has two linear branched chains, and the branched point is at a beta-carbon position or a gamma-carbon position; the difference of the carbon number of the two branched chains of the aliphatic long-chain branched unit alcohol is 2. The aliphatic long-chain branched unit alcohol is liquid at normal temperature (20-25 ℃). Examples of the aliphatic long-chain branched monoalcohol are 2-octyldodecanol and 2-nonyltridecanol. The triazine ring structure of the trimethylated melamine formaldehyde resin is beneficial to improving the salt spray resistance of the coating; the aliphatic long-chain branching unit alcohol contributes to the improvement of the gloss of the coating film.
Further, the aliphatic long-chain branched unit alcohol is 2-octyldodecanol or 2-nonyltridecanol.
Further, the cardanol phenolic aldehyde amine is a mixture of a compound C and a compound D, and the mass ratio of the compound C to the compound D is 2.5-3.5: 1. The cardanol structural unit can remarkably improve the salt spray resistance of the coating film, and is favorable for balancing the weather resistance and the corrosion resistance of the coating film.
Further, the compound C is prepared by reacting cardanol, diethylenetriamine, paraformaldehyde and tert-carbonic acid glycidyl ester; the compound D is prepared by reacting cardanol, m-xylylenediamine and butyraldehyde. M-xylylenediamine contributes to the improvement of the salt spray resistance of the coating film.
Further, the curing agent is an aliphatic isocyanate trimer.
Further, the diluent is formed by mixing propylene glycol diacetate, butyl acetate and xylene according to the mass ratio of 1:1: 1.
The technical scheme adopted for further solving the technical problems is as follows: a preparation method of a slow polyurea primer-topcoat coating comprises the following steps:
(1) synthesis of Polymer A: adding 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane into a round-bottom flask provided with a stirrer, a heating sleeve, nitrogen, a dropping funnel and a thermocouple, dropping dicacardanol maleate into the flask under the control of temperature, heating the flask after the dropping is finished, cooling the flask to room temperature, and standing the flask; heating again, and dropwise adding tert-carbonic acid glycidyl ester; heating for the third time after the dripping is finished to obtain the product;
(2) synthesis of cardanol-based phenolic aldehyde amine C: adding cardanol and diethylenetriamine into a three-neck round-bottom flask provided with a stirrer, a condenser and a thermocouple, uniformly stirring and heating; then adding paraformaldehyde, and heating again after the addition is finished to perform reaction; then carrying out vacuum dehydration under a stirring state, cooling, dropwise adding the tertiary carbonic acid glycidyl ester by using a peristaltic pump, and carrying out heat preservation after dropwise adding is finished;
(3) synthesis of cardanol-based phenolic aldehyde amine D: adding cardanol and m-xylylenediamine into a three-neck round-bottom flask provided with a stirrer, a condenser and a thermocouple, uniformly stirring, heating, and dropwise adding butyraldehyde into the mixture; after the feeding is finished, preserving the heat, heating, and collecting distillate in the heating process; preserving heat again, heating again, and cooling to obtain the final product;
(4) preparation of the slow polyurea primer-topcoat coating: mixing polyaspartic acid ester resin formed by mixing a polymer A and a polymer B, trimethyl etherified melamine formaldehyde resin, cardanol phenolic aldehyde amine C obtained in the step (2) and cardanol phenolic aldehyde amine D obtained in the step (3) to form cardanol phenolic aldehyde amine, barium sulfate, medium yellow, iron oxide red, silicon dioxide, a defoaming agent, a leveling agent, a dispersing agent, an ultraviolet light absorbing agent and a solvent, and dispersing and grinding to obtain a base material; and mixing the base material and the curing agent to obtain the adhesive.
Further, in the step (1), the dropping temperature of the maleic acid dicarballyl ester is less than or equal to 50 ℃; the temperature of the temperature rise is 55-60 ℃; the temperature rise time is 5-8 h; the standing time is more than or equal to 12 hours; the temperature for reheating is 60-65 ℃, and the time for dripping the tertiary carbonic acid glycidyl ester is less than or equal to 30 min; the temperature of the third temperature rise is 60-75 ℃, and the time of the third temperature rise is more than or equal to 2 hours;
further, in the step (2), heating to 58-62 ℃; the temperature for reheating is 96-100 ℃, and the reaction time is more than or equal to 2 hours; the vacuum dehydration is carried out under the conditions that the vacuum degree is 0.085-0.095 and the temperature is 95-105 ℃, and the vacuum dehydration time is 50-70 min; the temperature for cooling is 68-72 ℃; the speed of dripping the tertiary carbonic acid glycidyl ester by using the peristaltic pump is 2-3 mL/min, the heat preservation temperature is 78-82 ℃, and the heat preservation time is more than or equal to 2 hours;
further, in the step (3), the heating temperature is 47-50 ℃, and the time for dripping butyraldehyde is less than or equal to 60 min; the heat preservation temperature is 47-54 ℃, and the heat preservation time is more than or equal to 60 min; the temperature for raising the temperature is 150-160 ℃; the temperature for heat preservation is 160-165 ℃ again, and the heat preservation time is more than or equal to 20 min; the temperature for secondary heating is 165-170 ℃; the cooling time is more than or equal to 45 min.
Compared with the prior similar products, the coating has longer construction pot life and shorter surface drying time: the construction working life is more than or equal to 4 hours, and the surface drying time is 35-60 min; the product is sprayed on the surface of a metal or concrete substrate, and a coating film with high drying speed and excellent weather resistance and salt spray resistance can be formed.
Detailed Description
The present invention will be further described with reference to the following examples.
Desmophen NH1420 used in the examples was obtained from Covestro, Germany, and DESMODUR N3390 BA/SN curing agent (HDI trimer) was obtained from Covestro, Germany; the F420 resin was purchased from sezukihan corporation.
Other chemicals used in the examples, unless otherwise specified, were obtained from conventional commercial sources.
Example 1
The slow-rate polyurea primer-topcoat coating of the embodiment is prepared by mixing a base material and 35.1 parts by mass of DESMODUR N3390 BA/SN curing agent (HDI tripolymer, Covestro, Germany); the base material was prepared by compounding 21.0 parts by mass of polyaspartic acid ester resin (of which 18.0 parts by mass of the polymer a prepared in reference example 1 and 3.0 parts by mass of the F420 resin), 3.0 parts by mass of trimethylated melamine formaldehyde resin (80% solids content), 18.0 parts by mass of cardanol-based phenalkamine (including 13.0 parts by mass of the compound C prepared in reference example 2 and 5.0 parts by mass of the compound D prepared in reference example 3), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of medium yellow, 0.3 parts by mass of iron red, 0.5 parts by mass of fumed silica, 0.3 part by mass of an antifoaming agent, 0.4 part by mass of a leveling agent, 0.4 part by mass of a dispersing agent, 0.5 part by mass of an ultraviolet absorbing agent, and 9.5 parts by mass of a solvent.
The preparation method of the slow polyurea primer-topcoat coating comprises the following steps:
(1) synthesis of Polymer A: 238g of 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane (1.0mol of DMDC) were placed in a 2-liter round-bottomed flask equipped with stirrer, heating mantle, nitrogen, dropping funnel, thermocouple and 1307.2g of dicacardanol maleate (1.9mol) were added dropwise in 2h at a temperature of not more than 50 ℃. After the dropwise addition, the temperature is raised to 60 ℃ and maintained for 7h, and the mixture is cooled to room temperature and then kept stand for 12 h. Heating to 65 ℃, and dripping 22.8g of tertiary carbonic acid glycidyl ester (0.1mol) within 30 min; after the dripping is finished, the temperature is raised to 75 ℃ and maintained for 2 hours, thus obtaining the liquid.
(2) Synthesis of cardanol-based phenolic aldehyde amine C: adding 304g (1.0mol) of cardanol and 145g (1.4mol) of diethylenetriamine into a 1L three-neck round-bottom flask provided with a stirrer, a condenser and a thermocouple, uniformly stirring, and heating to 58-62 ℃; slowly adding 39g (1.3mol) of paraformaldehyde, heating to 96-100 ℃ after the addition is finished, and reacting for 2 hours; and dehydrating at 95-105 ℃ for 50-70 min under the vacuum degree of 0.085-0.095 in a stirring state, cooling to 68-72 ℃, dropwise adding 228g (1.0mol) of tertiary carbonic acid glycidyl ester by using a peristaltic pump at the speed of 2.60mL/min, and preserving heat for 2h at 78-82 ℃ after dropwise adding is finished, thus obtaining the product.
(3) Synthesis of cardanol-based phenolic aldehyde amine D: 304g (1.0mol) cardanol and 272g (2mol) m-xylylenediamine were added to a 1L three-necked round-bottomed flask equipped with a stirrer, a condenser, and a thermocouple, stirred well, and the flask contents were purged with nitrogen and heated to 48 ℃; keeping the temperature at 47-50 ℃, and dropwise adding 144g (2mol) of butyraldehyde into the mixture within 60 min; after the feeding is finished, keeping the temperature at 47-54 ℃ for 60min, and then heating to 160 ℃; collecting all distillate in the temperature rising process; and keeping the temperature at 160 ℃ for 20min, then heating to 170 ℃, cooling the content in the flask after 45min, and discharging to obtain the product.
(4) Preparation of the slow polyurea primer-topcoat coating: 21.0 parts by mass of polyaspartic acid ester resin (of which 18.0 parts by mass of the polymer a prepared in reference example 1 and 3.0 parts by mass of the F420 resin), 3.0 parts by mass of trimethylated melamine formaldehyde resin (80% solids), 18.0 parts by mass of cardanol-based phenol aldehyde amine (containing 13.0 parts by mass of the compound C prepared in reference example 2 and 5.0 parts by mass of the compound D prepared in reference example 3), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of medium yellow, 0.3 part by mass of iron red, 0.5 part by mass of fumed silica, 0.3 part by mass of an antifoaming agent, 0.4 part by mass of a leveling agent, 0.4 part by mass of a dispersing agent, 0.5 part by mass of an ultraviolet absorbing agent, and 9.5 parts by mass of a solvent were mixed and dispersed and ground to a fineness of less than 30 μm, thereby obtaining a base material. Mixing the base material with 35.1 parts by mass of DESMODUR N3390 BA/SN curing agent (HDI tripolymer, Covestro Germany) to obtain the adhesive.
Example 2
The slow-rate polyurea primer-topcoat coating of the embodiment is prepared by mixing a base material and 34.8 parts by mass of DESMODUR N3390 BA/SN curing agent (HDI trimer, Covestro, Germany); the base material is prepared by mixing 21.0 parts by mass of polyaspartic acid ester resin (wherein 18.0 parts by mass of the polymer A and 3.0 parts by mass of the F420 resin), 3.0 parts by mass of trimethyletherified melamine formaldehyde resin (80% solid content), 18.0 parts by mass of cardanol phenolic aldehyde amine (containing 13.5 parts by mass of the compound C and 4.5 parts by mass of the compound D), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of mesogen, 0.3 part by mass of iron oxide red, 0.5 part by mass of fumed silica, 0.3 part by mass of a defoaming agent, 0.4 part by mass of a leveling agent, 0.4 part by mass of a dispersing agent, 0.5 part by mass of an ultraviolet absorbing agent and 9.5 parts by mass of a solvent.
The preparation method of the slow polyurea primer-topcoat coating comprises the following steps: the synthesis of polymer a, cardanol-based phenalkamine C and cardanol-based phenalkamine D are the same as in example 1, differing only in that:
preparation of the slow polyurea primer-topcoat coating: 21.0 parts by mass of polyaspartic acid ester resin (wherein 18.0 parts by mass of the polymer A and 3.0 parts by mass of the F420 resin), 3.0 parts by mass of trimethyletherified melamine formaldehyde resin (80% of solid), 18.0 parts by mass of cardanol-based phenol aldehyde amine (containing 13.5 parts by mass of the compound C and 4.5 parts by mass of the compound D), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of mesogen, 0.3 part by mass of iron oxide red, 0.5 part by mass of fumed silica, 0.3 part by mass of a defoaming agent, 0.4 part by mass of a leveling agent, 0.4 part by mass of a dispersing agent, 0.5 part by mass of an ultraviolet absorbing agent and 9.5 parts by mass of a solvent are mixed, dispersed and ground to a fineness of less than 30 mu m, and a base material. The base material was mixed with 34.8 parts by mass of DESMODUR N3390 BA/SN curing agent (HDI trimer, Covestro, Germany) to prepare a coating film.
Example 3
The slow-rate polyurea primer-topcoat coating of the embodiment is prepared by mixing a base material and 34.6 parts by mass of DESMODUR N3390 BA/SN curing agent (HDI tripolymer, Covestro, Germany); the base material is prepared by mixing 21.0 parts by mass of polyaspartic acid ester resin (wherein 18.0 parts by mass of the polymer A and 3.0 parts by mass of the F420 resin), 3.0 parts by mass of trimethyletherified melamine formaldehyde resin (80% solid content), 18.0 parts by mass of cardanol phenolic aldehyde amine (containing 13.9 parts by mass of the compound C and 4.1 parts by mass of the compound D), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of mesogen, 0.3 part by mass of iron oxide red, 0.5 part by mass of fumed silica, 0.3 part by mass of a defoaming agent, 0.4 part by mass of a leveling agent, 0.4 part by mass of a dispersing agent, 0.5 part by mass of an ultraviolet absorbing agent and 9.5 parts by mass of a solvent.
The preparation method of the slow polyurea primer-topcoat coating comprises the following steps: the synthesis of polymer a, cardanol-based phenalkamine C and cardanol-based phenalkamine D are the same as in example 1, differing only in that:
preparation of the slow polyurea primer-topcoat coating: 21.0 parts by mass of polyaspartic acid ester resin (wherein 18.0 parts by mass of the polymer A and 3.0 parts by mass of the F420 resin), 3.0 parts by mass of trimethyletherified melamine formaldehyde resin (80% of solid), 18.0 parts by mass of cardanol-based phenol aldehyde amine (containing 13.9 parts by mass of the compound C and 4.1 parts by mass of the compound D), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of mesogen, 0.3 part by mass of iron oxide red, 0.5 part by mass of fumed silica, 0.3 part by mass of a defoaming agent, 0.4 part by mass of a leveling agent, 0.4 part by mass of a dispersing agent, 0.5 part by mass of an ultraviolet absorbing agent and 9.5 parts by mass of a solvent are mixed, dispersed and ground to a fineness of less than 30 mu m, and a base material. The base material was mixed with 34.6 parts by mass of DESMODUR N3390 BA/SN curing agent (HDI trimer, Covestro, Germany) to prepare a coating film.
Comparative example 1
21.0 parts by mass of polyaspartic acid ester resin (wherein 18.0 parts by mass of Desmophen NH1520 and 3.0 parts by mass of F420 resin), 3.0 parts by mass of trimethylated melamine formaldehyde resin (80% solid content), 18.0 parts by mass of cardanol-based phenol aldehyde amine (containing 13.5 parts by mass of compound C and 4.5 parts by mass of compound D), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of medium yellow, 0.3 part by mass of iron red, 0.5 part by mass of fumed silica, 0.3 part by mass of defoaming agent, 0.4 part by mass of leveling agent, 0.4 part by mass of dispersing agent, 0.5 part by mass of ultraviolet absorber and 9.5 parts by mass of solvent are mixed and dispersed and ground to a fineness of less than 30 mu m, thus obtaining the base material component. The base material was mixed with 43.6 parts by mass of Desmodur N3390 BA/SN curing agent (HDI trimer, Covestro, Germany) to prepare a coating film.
Comparative example 2
21.0 parts by mass of polyaspartic acid ester resin (wherein 18.0 parts by mass of the polymer A and 3.0 parts by mass of the F420 resin), 2.8 parts by mass of Resimene 717 (84% solid content, INEOS company), 18.0 parts by mass of cardanol phenolic aldehyde amine (containing 13.5 parts by mass of the compound C and 4.5 parts by mass of the compound D), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of mesogen, 0.3 part by mass of iron oxide red, 0.5 part by mass of fumed silica, 0.3 part by mass of an antifoaming agent, 0.4 part by mass of a leveling agent, 0.4 part by mass of a dispersing agent, 0.5 part by mass of an ultraviolet absorber and 9.5 parts by mass of a solvent are mixed, dispersed and ground to a fineness of less than 30 μm, thereby obtaining a base material component. The base material was mixed with 35.2 parts by mass of DESMODUR N3390 BA/SN curing agent (HDI trimer, Covestro, Germany) to prepare a coating film.
Comparative example 3
21.0 parts by mass of polyaspartic acid ester resin (wherein 18.0 parts by mass of the polymer A and 3.0 parts by mass of the F420 resin), 3.0 parts by mass of trimethyletherified melamine formaldehyde resin (80% of solid), 18.0 parts by mass of cardanol phenol aldehyde amine NX-2015 (Kadarley), 20.3 parts by mass of ultrafine barium sulfate, 23.0 parts by mass of medium yellow, 0.3 part by mass of iron oxide red, 0.5 part by mass of fumed silica, 0.3 part by mass of an antifoaming agent, 0.4 part by mass of a leveling agent, 0.4 part by mass of a dispersing agent, 0.5 part by mass of an ultraviolet absorber and 9.5 parts by mass of a solvent are mixed, and the mixture is dispersed and ground to a fineness of less than 30 mu m, so as to obtain a base material component. The base material was mixed with 19.6 parts by mass of DESMODUR N3390 BA/SN curing agent (HDI trimer, Covestro, Germany) to prepare a coating film.
Paint and coating film tests of examples and comparative examples:
comparative example 1 shows that the maleic acid dicacardol ester can effectively prolong the construction pot life of the coating and improve the gloss of the coating; comparative example 2 shows that the low molecular alcohol solvent of the common amino resin reduces the crosslinking density of the coating film, reduces the gloss and the weather resistance, and the aliphatic long-chain branched unit alcohol obviously improves the gloss; comparative example 3 shows that the remaining primary amine of the unmodified cardanol phenolic aldehyde amine obviously shortens the pot life of the coating; examples 1-3 show that the construction pot life of the slow polyurea coating is as long as 4 hours, the surface drying time is within the range of 45-55 min, the gloss (60 ℃) is higher (more than 90%), the weather resistance and the salt spray resistance of a coating film are excellent, and the surface drying time of the coating film can be effectively shortened and the gloss of the coating film can be improved by increasing the using amount of the compound D.
Claims (11)
1. The slow polyurea primer-topcoat coating is characterized in that: is prepared by mixing a base material, a curing agent and a diluent; the base material consists of polyaspartic acid ester resin, trimethylated melamine formaldehyde resin, cardanol phenolic aldehyde amine, pigment, filler, auxiliary agent and solvent;
the polyaspartic acid ester resin is formed by mixing a polymer A and a polymer B according to the mass ratio of 5-7: 1;
the polymer A is prepared by reacting 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, maleic acid dicarballyl ester and tertiary carbonic acid glycidyl ester according to the molar ratio of 1.0: 1.75-1.95: 0.05-0.25;
the polymer B is Desmophen NH1420 or F420 resin.
2. The slow polyurea topcoat coating of claim 1, wherein: the solid content of the trimethyl etherified melamine formaldehyde resin is 80%, and the solvent is aliphatic long-chain branched unit alcohol.
3. The slow polyurea topcoat coating of claim 2, wherein: the aliphatic long-chain branched unit alcohol is 2-octyldodecanol or 2-nonyltridecanol.
4. The slow polyurea primer-topcoat coating of any one of claims 1 to 3, wherein: the cardanol phenolic aldehyde amine is a mixture of a compound C and a compound D, and the mass ratio of the compound C to the compound D is 2.5-3.5: 1;
the compound C is prepared by reacting cardanol, diethylenetriamine, paraformaldehyde and tert-carbonic acid glycidyl ester;
the compound D is prepared by reacting cardanol, m-xylylenediamine and butyraldehyde.
5. The slow polyurea primer-topcoat coating of any one of claims 1 to 3, wherein: the curing agent is aliphatic isocyanate trimer; the diluent is prepared by mixing propylene glycol diacetate, butyl acetate and xylene according to the mass ratio of 1:1: 1.
6. The slow polyurea topcoat coating of claim 4, wherein: the curing agent is aliphatic isocyanate trimer; the diluent is prepared by mixing propylene glycol diacetate, butyl acetate and xylene according to the mass ratio of 1:1: 1.
7. A method of preparing the slow polyurea primer-topcoat coating of claim 4, wherein: the method comprises the following steps:
(1) synthesis of Polymer A: adding 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane into a round-bottom flask provided with a stirrer, a heating sleeve, nitrogen, a dropping funnel and a thermocouple, dropping dicacardanol maleate into the flask under the control of temperature, heating the flask after the dropping is finished, cooling the flask to room temperature, and standing the flask; heating again, and dropwise adding tert-carbonic acid glycidyl ester; heating for the third time after the dripping is finished to obtain the product;
(2) synthesis of cardanol-based phenolic aldehyde amine C: adding cardanol and diethylenetriamine into a three-neck round-bottom flask provided with a stirrer, a condenser and a thermocouple, uniformly stirring and heating; then adding paraformaldehyde, raising the temperature again after the addition is finished, carrying out reaction, then carrying out vacuum dehydration under a stirring state, cooling, dropwise adding the tertiary carbonic acid glycidyl ester by using a peristaltic pump, and carrying out heat preservation after the dropwise adding is finished;
(3) synthesis of cardanol-based phenolic aldehyde amine D: adding cardanol and m-xylylenediamine into a three-neck round-bottom flask provided with a stirrer, a condenser and a thermocouple, uniformly stirring, heating, and dropwise adding butyraldehyde into the mixture; after the feeding is finished, preserving the heat, heating, and collecting distillate in the heating process; preserving heat again, heating again, and cooling to obtain the final product;
(4) preparation of the slow polyurea primer-topcoat coating: mixing polyaspartic acid ester resin formed by mixing a polymer A and a polymer B, trimethyl etherified melamine formaldehyde resin, cardanol phenolic aldehyde amine C obtained in the step (2) and cardanol phenolic aldehyde amine D obtained in the step (3) to form cardanol phenolic aldehyde amine, barium sulfate, medium yellow, iron oxide red, silicon dioxide, a defoaming agent, a leveling agent, a dispersing agent, an ultraviolet light absorbing agent and a solvent, and dispersing and grinding to obtain a base material; and mixing the base material and the curing agent to obtain the adhesive.
8. The method of preparing a slow polyurea primer-topcoat coating of claim 7, wherein: in the step (1), the dropping temperature of the maleic acid dicacardol ester is less than or equal to 50 ℃; the temperature of the temperature rise is 55-60 ℃; the temperature rise time is 5-8 h; the standing time is more than or equal to 12 hours; the temperature for reheating is 60-65 ℃, and the time for dripping the tertiary carbonic acid glycidyl ester is less than or equal to 30 min; the temperature of the third temperature rise is 60-75 ℃, and the time of the third temperature rise is more than or equal to 2 hours.
9. The method of preparing a slow polyurea primer-topcoat coating of claim 7 or 8, wherein: in the step (2), heating to 58-62 ℃; the temperature for reheating is 96-100 ℃, and the reaction time is more than or equal to 2 hours; the vacuum dehydration is carried out under the conditions that the vacuum degree is 0.085-0.095 and the temperature is 95-105 ℃, and the vacuum dehydration time is 50-70 min; the temperature for cooling is 68-72 ℃; the speed of dripping the tertiary carbonic acid glycidyl ester by using the peristaltic pump is 2-3 mL/min, the heat preservation temperature is 78-82 ℃, and the heat preservation time is more than or equal to 2 hours.
10. The method of preparing a slow polyurea primer-topcoat coating of claim 7 or 8, wherein: in the step (3), the heating temperature is 47-50 ℃, and the time for dripping butyraldehyde is less than or equal to 60 min; the heat preservation temperature is 47-54 ℃, and the heat preservation time is more than or equal to 60 min; the temperature of the heating is 150-160 ℃, the temperature of the secondary heat preservation is 160-165 ℃, and the heat preservation time is more than or equal to 20 min; the temperature for secondary heating is 165-170 ℃; the cooling time is more than or equal to 45 min.
11. The method of preparing a slow polyurea primer-topcoat coating of claim 9, wherein: in the step (3), the heating temperature is 47-50 ℃, and the time for dripping butyraldehyde is less than or equal to 60 min; the heat preservation temperature is 47-54 ℃, and the heat preservation time is more than or equal to 60 min; the temperature of the heating is 150-160 ℃, the temperature of the secondary heat preservation is 160-165 ℃, and the heat preservation time is more than or equal to 20 min; the temperature for secondary heating is 165-170 ℃; the cooling time is more than or equal to 45 min.
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