CN111793420A - Modified polyaspartic acid ester polyurea coating and preparation method thereof - Google Patents
Modified polyaspartic acid ester polyurea coating and preparation method thereof Download PDFInfo
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- 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
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Abstract
The invention belongs to the technical field of coatings, and particularly relates to a modified polyaspartic acid ester polyurea coating and a preparation method thereof, wherein the coating comprises a component A and a component B, and the component A, B is prepared and stored independently. The A component comprises isocyanate and/or polymer of isocyanate; the component B comprises 20-75 parts of organic silicon and epoxy double modified polyaspartic acid ester resin, 5-35 parts of filler, 0.1-5 parts of pigment, 0.5-10 parts of auxiliary agent and 5-30 parts of solvent. The organic silicon unit and the epoxy unit are introduced into the polyaspartic acid ester resin structure of the coating disclosed by the invention, so that the novel polyurea coating with excellent low-temperature flexibility, bonding strength, weather resistance and mechanical properties is obtained.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a modified polyaspartic acid ester polyurea coating and a preparation method thereof.
Background
The polyurea coating is a pollution-free high-performance environment-friendly material, is a novel material developed in recent years after environment-friendly coatings such as high-solid coatings, water-based coatings, photo-curing coatings, powder coatings and the like, and is widely applied to the field of material protection. After the first-generation aromatic polyurea coating and the second-generation aliphatic polyurea, the third-generation polyaspartic ester polyurea converts the active functional group primary amino group in the traditional polyurea into a secondary amino group, the reaction activity in the polyaspartic ester is greatly reduced under the combined action of an electronic effect and a steric effect, the gelation time is controllable due to the special molecular structure of the polyaspartic ester, and the construction can be carried out by using the traditional spraying mode, such as air spraying, airless spraying and the like. In addition, the polyaspartic acid ester polyurea coating has the performances of excellent weather resistance, good surface leveling property, high hardness and the like, and still has certain defects in practical application, such as poor low-temperature flexibility, poor adhesion with a base material and the like.
In order to solve some defects of the polyaspartic ester polyurea coating, Chinese patent document CN106854428B proposes that polyaspartic ester resin modified by hydrogenated epoxy resin and HDI trimer curing agent are used as main film forming substances, and a sheet-shaped preservative composite system is adopted to improve the compactness of a paint film and improve the medium resistance and the corrosion resistance of the paint film. The flexible polyurea heavy-duty anticorrosive coating is a two-component system, has NCO index of 1.05-1.1, integrates a bottom surface and a base surface, is high in curing speed and tensile strength, has certain hardness and flexibility, is strong in adhesive force with a base material, and is still insufficient in low-temperature flexibility. Chinese patent document CN107298930A proposes an organosilicon-polyurea self-layering coating, which comprises two parts, namely organosilicon modified polyurethane curing agent component preparation and silicon-containing resin component preparation, wherein a gradual transition layer is formed by an organosilicon resin component and a polyurea base material in the coating curing process, a polyurea chain segment is gathered on an inner film layer, and an organosilicon chain segment is gathered on an outer film layer.
Disclosure of Invention
The invention aims to solve the problems of poor low-temperature flexibility and poor adhesion with a base material of a polyaspartic ester polyurea coating, and provides a modified polyaspartic ester polyurea coating.
In order to achieve the above purpose, the invention provides the following technical scheme:
a modified polyaspartic acid ester polyurea coating comprises a component A and a component B, which are calculated according to the parts by weight,
the component A comprises the following substances: an isocyanate and/or a polymer of said isocyanate.
The component B comprises the following substances: 20-75 parts of organic silicon and epoxy double modified polyaspartic acid ester resin, 5-35 parts of filler, 0.1-5 parts of pigment, 0.5-10 parts of auxiliary agent and 5-30 parts of solvent.
According to the modified polyaspartic ester polyurea coating, the organic silicon unit and the epoxy unit are introduced into the structure of polyaspartic ester resin, so that the performance of the coating has the performance of polyaspartic ester and partial performances of organic silicon and epoxy materials, the defects and shortcomings of the polyaspartic ester resin, the organic silicon resin and the epoxy resin in the process of single use are overcome, meanwhile, the organic silicon unit forms a molecular layer with extremely high density and low surface energy, the water resistance, the dirt resistance and other performances of the surface of a paint film are greatly improved, and the modified polyaspartic ester polyurea coating has higher service performance.
In a preferable embodiment of the present invention, the functionality of the isocyanate in the component A is 2 to 3.
As a preferable embodiment of the present invention, the isocyanate in the a component includes any one of HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), MDI (diphenylmethane diisocyanate), TDI (toluene diisocyanate), and the like; the polymer of the isocyanate comprises any one of HDI trimer, IPDI trimer, MDI trimer and the like. Preferably, the isocyanate is Desmodur N3300 available from Bayer or Basonat HI 190B/S available from Basff.
As a preferable scheme of the invention, the organosilicon and epoxy double modified polyaspartic ester resin is prepared from the following materials in parts by weight: 10-50 parts of polyamine, 5-35 parts of maleic ester, 5-20 parts of epoxy resin, 5-20 parts of silane coupling agent, 5-20 parts of polyisocyanate and 5-15 parts of organic solvent.
As a preferable scheme of the invention, the preparation of the organosilicon and epoxy double modified polyaspartic acid ester resin comprises the following steps:
(1) preparation of polyaspartic acid ester resin: adding polyamine into a reaction kettle filled with protective gas, stirring, heating to 65-80 ℃, dropwise adding maleic acid ester into the reaction kettle, reacting for 8-25 h, and cooling to obtain polyaspartic acid ester resin;
preparation of a prepolymer: adding a silane coupling agent and maleic ester into a reaction kettle filled with protective gas, stirring, heating to 55-75 ℃, and reacting for 10-15 hours; adding polyisocyanate, reacting for 1-4 h at the temperature of 60-70 ℃, cooling to obtain a prepolymer, and dissolving the prepolymer in an organic solvent for later use;
(2) adding the polyaspartic acid ester resin obtained in the step (1), epoxy resin and an organic solvent into a reaction kettle filled with protective gas, uniformly mixing, dropwise adding the prepolymer dissolved in the organic solvent obtained in the step (1) while stirring, heating to 65-80 ℃, reacting for 2-6 h, and cooling to obtain the organic silicon and epoxy double-modified polyaspartic acid ester resin.
In a preferred embodiment of the present invention, the polyamine includes any one of an aliphatic primary diamine or an amino-terminated polyether.
As a preferred embodiment of the present invention, the aliphatic primary diamine comprises hexamethylenediamine, IPDA (isophoronediamine), H12MDA (4, 4' -diaminodicyclohexylmethane) and MACM (bis (4-dimethylamino-cyclohexyl) methane).
The preferable scheme of the invention is that the amino-terminated polyether comprises any one of amino-terminated polyoxypropylene ether, amino-terminated polyoxyethylene ether and amino-terminated polytetramethylene ether, the range of the functionality is 2-3, and the molecular weight range is 230-3000.
In a preferred embodiment of the present invention, the maleate includes any one of dimethyl maleate, diethyl maleate, and dibutyl maleate.
In a preferred embodiment of the present invention, the silane coupling agent includes any one of amino functional silane, methacryloxy functional silane, vinyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and methyltriethoxysilane.
As a preferable embodiment of the present invention, the polyisocyanate includes any one of IPDI trimer, HDI trimer and TDI (toluene diisocyanate) trimer.
In a preferred embodiment of the present invention, the epoxy resin includes any one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and aliphatic glycidyl amine type epoxy resin, and preferably, the epoxy resin is designated by the designations E20, E44, and E51.
In a preferred embodiment of the present invention, the organic solvent is one or more of ester, ketone and benzene, preferably, butyl acetate, acetone, benzene, xylene, etc.
As a preferable scheme of the invention, the filler is one or more of calcium carbonate, kaolin, glass flakes, talcum powder, silicon micropowder, mica powder and barium sulfate. Preferably, the filler is spherical and has a particle size of 50-1000 meshes.
As a preferred scheme of the invention, the pigment is one or more of titanium dioxide, iron black, carbon black, iron yellow or iron red.
According to the preferable scheme of the invention, the auxiliary agent comprises, by weight, 0.1-5 parts of a dispersing agent, 0.1-5 parts of an antifoaming agent, 0.1-5 parts of a leveling agent and 0.1-5 parts of an anti-settling agent.
As a preferable scheme of the invention, the dispersant is one or more of acrylate high molecular type dispersant, polyhexamethylene lactone polyol-polyethyleneimine segmented copolymer type dispersant, polyurethane or polyester high molecular type dispersant, so that good affinity to inorganic and organic pigments and fillers can be realized, and the inorganic and organic pigments and fillers can be well dispersed. Preferably, the dispersant is BYK company BYK-163.
As a preferred scheme of the invention, the flatting agent is one or more of polyether polyester modified organosilicone, alkyl modified organosilicone, acrylate and fluorine modified acrylate flatting agents; preferably, the leveling agent is EFKA3600 of Dutch EFKA company, CAB381-0.1 of Eastman company and CAB 551-0.1.
In a preferred embodiment of the present invention, the defoaming agent is one or more of mineral oil, polyorganosiloxane, silicone defoaming agent, polyether defoaming agent, and the like. Preferably, the antifoaming agent is Defom5400, Defom5500, teuxe, ltd EFKA2038, teh.
As a preferable scheme of the invention, the anti-settling agent is one or more of fumed silica, organic bentonite, polyolefin wax and castor oil derivative anti-settling agents.
According to another aspect of the present invention, there is provided a method of preparing a modified polyaspartate polyurea coating, wherein A, B components are prepared separately,
preparation of the component A: adding isocyanate and/or polymer of the isocyanate into a container, and uniformly stirring to obtain a component A;
preparation of the component B: adding the organosilicon and epoxy double-modified polyaspartic acid ester resin into a container, respectively adding the filler, the pigment, the auxiliary agent and the solvent, and uniformly stirring and dispersing to obtain a component B;
and (2) mixing the component A and the component B according to the mass ratio of 1: 1-5, and uniformly stirring to obtain the modified polyaspartic acid ester polyurea coating.
As a preferable scheme of the invention, the rotation speed of stirring in the preparation of the component A is 500-1500 rpm, and the time is 5-10 min.
As a preferable scheme of the invention, the rotation speed of stirring in the preparation of the component B is 1000-2500 rpm, and the time is 10-30 min.
As a preferable scheme of the invention, the coating is a two-component coating, A, B components are prepared and must be stored separately during storage, and A, B components are mixed according to the proportion when the coating is needed to be used. A. The component B reacts after being mixed at room temperature, and is solidified into a film after a period of time.
The modified polyaspartic acid ester polyurea coating and the preparation method thereof can be applied to concrete, metal, composite materials and the like, and can be used as an anticorrosive coating to form an anticorrosive coating after the surface of the material is coated.
Compared with the prior art, the invention has the beneficial effects that:
1. the modified polyaspartic acid ester polyurea coating introduces the organic silicon unit and the epoxy unit into the resin structure, so that the modified polyaspartic acid ester polyurea coating has the advantages of extremely strong low-temperature flexibility, aging resistance, radiation resistance, wear resistance, hydrophobicity and the like of the organic silicon unit, and the epoxy unit has small contractibility and good adhesion; on the other hand, the advantages of high strength, high wear resistance and the like of the polyaspartic ester polyurea are exerted, so that the modified polyaspartic ester polyurea coating has higher durability.
2. The paint disclosed by the invention has good low-temperature flexibility and good weather resistance, and can be used as an anticorrosive paint in low-temperature cold regions.
3. The preparation method of the coating is simple, good in controllability, low in cost, capable of being prepared in batches and suitable for industrial production.
Drawings
FIG. 1 shows an infrared spectrum of a dual modified poly (aspartic ester) containing organosilicon and epoxy.
Detailed Description
The present invention will be described in further detail with reference to test examples and specific embodiments. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.
The raw material components and the weight parts of the raw materials of the organosilicon and epoxy double modified polyaspartic ester resin of the invention in the examples 1-4 and the comparative examples 1-3 are shown in the table 1.
TABLE 1 examples 1 to 4 and comparative examples 1 to 3 raw material components and parts by weight of raw materials
Note: in the table, "-" indicates that the raw material was not added.
Example 1
Adding 170 parts by weight of amino-terminated polyether D2000 into a reaction kettle filled with nitrogen, stirring and heating to 75 ℃, dropwise adding 337 parts by weight of dimethyl maleate into the reaction kettle, reacting at 80 ℃ for 16 hours after dropwise adding, and cooling to normal temperature to obtain the polyaspartic acid ester resin. Adding 80 parts by weight of silane coupling agent KH550 and 87 parts by weight of dimethyl maleate into another reaction kettle filled with nitrogen, stirring, and heating to 70 ℃ for reaction for 8 hours; and adding 170 parts by weight of IPDI tripolymer, reacting for 2 hours at the temperature of 70 ℃, cooling to normal temperature to obtain a prepolymer with-NCO active functional groups, and dissolving the prepolymer in butyl acetate for later use.
Adding 507 parts by weight of polyaspartic acid ester resin, 57 parts by weight of epoxy resin E44 and 75 parts by weight of butyl acetate into a reaction kettle filled with nitrogen, stirring and mixing uniformly, dropwise adding 337 parts by weight of prepolymer dissolved in 25 parts by weight of butyl acetate in advance while stirring, heating to 70 ℃ after dropwise adding, reacting for 3 hours, and cooling to normal temperature to obtain the organic silicon and epoxy double-modified polyaspartic acid ester resin 1.
And carrying out infrared spectrum test on the prepared organosilicon and epoxy double modified polyaspartic acid ester. Under the condition of room temperature, tabletting the potassium bromide solid under the pressure of 10MPa for 1min, then coating a small amount of sample on the potassium bromide tablet to prepare a sample, and measuring the sample on a Fourier infrared spectrometer, wherein the infrared test result is shown in figure 1.
Example 2
Adding 150 parts by weight of 4, 4' -diaminodicyclohexylmethane into a reaction kettle filled with nitrogen, stirring and heating to 75 ℃, dropwise adding 287 parts by weight of dibutyl maleate into the reaction kettle, reacting at 80 ℃ for 16 hours after dropwise adding, and cooling to normal temperature to obtain the polyaspartic ester resin. Adding 80 parts by weight of silane coupling agent KH550 and 87 parts by weight of dibutyl maleate into another reaction kettle filled with nitrogen, stirring, and heating to 70 ℃ for reaction for 8 hours; and adding 170 parts by weight of HDI trimer, reacting for 2 hours at the temperature of 70 ℃, cooling to normal temperature to obtain a prepolymer, and dissolving the prepolymer in butyl acetate for later use.
Adding 437 parts by weight of polyaspartic ester resin, 113 parts by weight of epoxy resin E44 and 75 parts by weight of butyl acetate into a reaction kettle filled with nitrogen, stirring and mixing uniformly, dropwise adding 337 parts by weight of prepolymer dissolved in 25 parts by weight of butyl acetate in advance while stirring, heating to 70 ℃ after dropwise adding, reacting for 3 hours, and cooling to normal temperature to obtain the organic silicon and epoxy double-modified polyaspartic ester resin 2.
Example 3
Adding 128 parts by weight of amino-terminated polyether D2000 into a reaction kettle filled with argon, stirring and heating to 75 ℃, dropwise adding 378 parts by weight of dibutyl maleate into the reaction kettle, and reacting at 80 ℃ for 16 hours after dropwise adding is finished to obtain the polyaspartic acid ester resin. Adding 80 parts by weight of silane coupling agent KH570 and 88 parts by weight of dibutyl maleate into another argon-filled reaction kettle, stirring, and heating to 70 ℃ for reaction for 8 hours; and adding 170 parts by weight of IPDI trimer, reacting for 2 hours at the temperature of 70 ℃, cooling to normal temperature to obtain a prepolymer, and dissolving the prepolymer in xylene for later use.
Adding 506 parts by weight of polyaspartic ester resin, 58 parts by weight of epoxy resin E44 and 75 parts by weight of dimethylbenzene into a reaction kettle filled with argon, stirring and mixing uniformly, dropwise adding 338 parts by weight of prepolymer dissolved in 25 parts by weight of dimethylbenzene in advance while stirring, heating to 70 ℃ after dropwise adding is finished, reacting for 3 hours, and cooling to normal temperature to obtain the organic silicon and epoxy double-modified polyaspartic ester resin 3.
Example 4
Adding 170 parts by weight of amino-terminated polyether D2000 into a reaction kettle filled with argon, stirring and heating to 75 ℃, dropwise adding 337 parts by weight of dimethyl maleate into the reaction kettle, reacting at 80 ℃ for 16 hours after dropwise adding, and cooling to normal temperature to obtain the polyaspartic acid ester resin. Adding 107 parts by weight of silane coupling agent KH570 and 117 parts by weight of dimethyl maleate into another argon-filled reaction kettle, stirring, and heating to 70 ℃ for reaction for 8 hours; adding 113 parts by weight of HDI tripolymer, reacting for 2 hours at the temperature of 70 ℃, cooling to normal temperature to obtain prepolymer, and dissolving the prepolymer in butyl acetate for later use.
Adding 507 parts by weight of polyaspartic acid ester resin, 57 parts by weight of epoxy resin E51 and 75 parts by weight of butyl acetate into a reaction kettle filled with argon gas, stirring and mixing uniformly, dropwise adding 337 parts by weight of prepolymer dissolved in 25 parts by weight of butyl acetate in advance while stirring, heating to 70 ℃ after dropwise adding is finished, reacting for 3 hours, and cooling to normal temperature to obtain the organic silicon and epoxy double-modified polyaspartic acid ester resin 4.
Comparative example 1
Adding 340 parts by weight of amino-terminated polyether D2000 into a reaction kettle filled with nitrogen, stirring and heating to 75 ℃, dropwise adding 660 parts by weight of dimethyl maleate into the reaction kettle, reacting at 80 ℃ for 16 hours after dropwise adding, and cooling to normal temperature to obtain the polyaspartic ester resin.
Comparative example 2
Adding 204 parts by weight of amino-terminated polyether D2000 into a reaction kettle filled with nitrogen, stirring and heating to 75 ℃, dropwise adding 404 parts by weight of dimethyl maleate into the reaction kettle, reacting at 80 ℃ for 16 hours after dropwise adding, and cooling to normal temperature to obtain the polyaspartic acid ester resin. Adding 608 parts by weight of polyaspartic ester resin, 68 parts by weight of epoxy resin E44, 204 parts by weight of IPDI trimer and 120 parts by weight of butyl acetate into a reaction kettle filled with nitrogen, stirring and mixing uniformly, heating to 70 ℃, reacting for 3 hours, and cooling to normal temperature to obtain the organic silicon modified polyaspartic ester resin.
Comparative example 3
Adding 180 parts by weight of amino-terminated polyether D2000 into a reaction kettle filled with nitrogen, stirring and heating to 75 ℃, dropwise adding 357 parts by weight of dimethyl maleate into the reaction kettle, reacting at 80 ℃ for 16 hours after dropwise adding, and cooling to normal temperature to obtain the polyaspartic acid ester resin. Adding 85 parts by weight of silane coupling agent KH550 and 92 parts by weight of dimethyl maleate into another reaction kettle filled with nitrogen, stirring, and heating to 70 ℃ for reaction for 8 hours; then adding 180 parts by weight of IPDI tripolymer, keeping the temperature at 70 ℃ for reaction for 2h, cooling to normal temperature to obtain a prepolymer with-NCO active functional groups, and dissolving the prepolymer in butyl acetate for later use.
537 parts by weight of polyaspartic acid ester resin and 81 parts by weight of butyl acetate are added into a reaction kettle filled with nitrogen, the mixture is stirred and mixed evenly, 357 parts by weight of prepolymer dissolved in 25 parts by weight of butyl acetate in advance is dripped while stirring, after the dripping is finished, the temperature is raised to 70 ℃, the reaction is carried out for 3 hours, and the epoxy modified polyaspartic acid ester resin is obtained after cooling to the normal temperature.
The components and parts by weight of the materials of the modified polyaspartic ester polyurea coating of the invention in examples 5-9 and comparative examples 4-6 are shown in Table 2.
TABLE 2 Components and parts by weight of materials of examples 5 to 9 and comparative examples 4 to 6
Note: in the table, "-" indicates that the raw material was not added.
Example 5
Weighing raw materials of a component B according to raw material components and a proportion of example 5 in Table 2, adding 1500 parts by weight of the organosilicone and epoxy double-modified polyaspartic acid ester resin 1 obtained in example 1 into a container, respectively adding 900 parts by weight of calcium carbonate with the particle size of 15 micrometers, 200 parts by weight of titanium dioxide, 75 parts by weight of a dispersing agent BYK-163, 25 parts by weight of a defoaming agent Defom5400, 30 parts by weight of a leveling agent EFKA3600, 70 parts by weight of fumed silica and 700 parts by weight of butyl acetate, mechanically stirring at a rotating speed of 1200rpm, and stirring for 20min until uniform dispersion is achieved to obtain the component B for later use;
1500 parts by weight of Desmodur N3300 of the component A is weighed, the component A is added into the mixed component B, and the mixture is stirred uniformly to obtain the modified polyaspartic ester polyurea coating.
Example 6
Weighing raw materials of a component B according to raw material components and a proportion of example 6 in Table 2, adding 1500 parts by weight of organosilicone and epoxy double-modified polyaspartic ester resin 2 obtained in example 2 into a container, respectively adding 500 parts by weight of calcium carbonate with the particle size of 15 micrometers, 400 parts by weight of talcum powder, 150 parts by weight of titanium dioxide, 50 parts by weight of dispersing agent BYK-163, 25 parts by weight of defoaming agent Defom5400, 15 parts by weight of flatting agent EFKA3600, 60 parts by weight of fumed silica and 800 parts by weight of dimethylbenzene, mechanically stirring at a rotating speed of 1500rpm, and stirring for 15min until uniform dispersion is achieved to obtain the component B for later use;
weighing 1500 parts by weight of Desmodur N3300 of the component A, adding the component A into the component B, mixing, and uniformly stirring to obtain the modified polyaspartic ester polyurea coating.
Example 7
Weighing raw materials of a component B according to raw material components and a proportion of example 7 in Table 2, adding 2000 parts by weight of the organic silicon and epoxy double modified polyaspartic acid ester resin 3 obtained in example 3 into a container, respectively adding 500 parts by weight of talcum powder with the particle size of 15 micrometers, 150 parts by weight of titanium dioxide, 50 parts by weight of dispersing agent BYK-163, 25 parts by weight of defoaming agent Defom5400, 25 parts by weight of flatting agent EFKA3600, 50 parts by weight of fumed silica and 700 parts by weight of butyl acetate, mechanically stirring at a rotating speed of 1500rpm, and stirring for 15min until uniform dispersion is achieved to obtain the component B for later use;
weighing 1000 parts by weight of Basonat HI 190B/S of the component A, adding the prepared component A into the component B, mixing, and uniformly stirring to obtain the modified polyaspartic acid ester polyurea coating.
Example 8
Weighing raw materials of a component B according to raw material components and a proportion of example 8 in Table 2, adding 1500 parts by weight of the organosilicone and epoxy double-modified polyaspartic acid ester resin 4 obtained in example 4 into a container, respectively adding 500 parts by weight of calcium carbonate with the particle size of 15 micrometers, 350 parts by weight of talcum powder, 200 parts by weight of titanium dioxide, 60 parts by weight of dispersing agent BYK-163, 20 parts by weight of defoaming agent Defom5400, 30 parts by weight of flatting agent EFKA3600, 40 parts by weight of fumed silica and 800 parts by weight of dimethylbenzene, mechanically stirring at a rotating speed of 1500rpm, and stirring for 15min until uniform dispersion is achieved to obtain the component B for later use;
weighing 1500 parts by weight of Basonat HI 190B/S of the component A, adding the component A into the mixed component B, and uniformly stirring to obtain the modified polyaspartic ester polyurea coating.
Example 9
Weighing raw materials of a component B according to raw material components and a proportion of example 9 in Table 2, adding 1500 parts by weight of the organosilicone and epoxy double-modified polyaspartic acid ester resin 3 obtained in example 3 into a container, respectively adding 1000 parts by weight of talcum powder with the particle size of 15 micrometers, 200 parts by weight of titanium dioxide, 50 parts by weight of dispersing agent BYK-163, 25 parts by weight of defoaming agent Defom5400, 25 parts by weight of flatting agent EFKA3600, 50 parts by weight of fumed silica and 900 parts by weight of butyl acetate, mechanically stirring at a rotating speed of 1500rpm, and stirring for 15min until uniform dispersion is achieved to obtain the component B for later use;
1250 parts by weight of Desmodur N3300 of the component A is weighed, the prepared component A is added into the component B to be mixed, and the mixture is uniformly stirred to obtain the modified poly aspartic ester polyurea coating.
Comparative example 4
Weighing the raw material of the component B according to the raw material components of comparative example 4 in the table 2, adding 1500 parts by weight of polyaspartic acid ester resin obtained in the comparative example 1 into a container, respectively adding 900 parts by weight of calcium carbonate with the particle size of 15 micrometers, 200 parts by weight of titanium dioxide, 75 parts by weight of dispersing agent BYK-163, 25 parts by weight of defoaming agent DEfom5400, 30 parts by weight of leveling agent EFKA3600, 70 parts by weight of fumed silica and 700 parts by weight of butyl acetate, mechanically stirring at the rotating speed of 1200rpm for 20min until uniform dispersion is achieved, and obtaining the component B for later use;
1500 parts by weight of Desmodur N3300 of the component A is weighed, the component A is added into the mixed component B, and the mixture is stirred uniformly to obtain the polyaspartic ester polyurea coating.
Comparative example 5
Weighing the raw material of the component B according to the raw material components of the comparative example 5 in the table 2, adding 1500 parts by weight of the organic silicon modified polyaspartic acid ester resin obtained in the comparative example 2 into a container, respectively adding 900 parts by weight of calcium carbonate with the particle size of 15 micrometers, 200 parts by weight of titanium dioxide, 75 parts by weight of dispersing agent BYK-163, 25 parts by weight of defoaming agent Defom5400, 30 parts by weight of leveling agent EFKA3600, 70 parts by weight of fumed silica and 700 parts by weight of butyl acetate, mechanically stirring at the rotating speed of 1200rpm for 20min to uniformly disperse to obtain the component B for later use;
1500 parts by weight of Desmodur N3300 of the component A is weighed, the component A is added into the mixed component B, and the mixture is uniformly stirred to obtain the organic silicon modified polyaspartic ester polyurea coating.
Comparative example 6
Weighing the raw material of the component B according to the raw material components of the comparative example 6 in the table 2, adding 1500 parts by weight of the epoxy modified polyaspartic acid ester resin obtained in the comparative example 3 into a container, respectively adding 900 parts by weight of calcium carbonate with the particle size of 15 micrometers, 200 parts by weight of titanium dioxide, 75 parts by weight of dispersing agent BYK-163, 25 parts by weight of defoaming agent Defom5400, 30 parts by weight of flatting agent EFKA3600, 70 parts by weight of fumed silica and 700 parts by weight of butyl acetate, mechanically stirring at the rotating speed of 1200rpm for 20min to uniformly disperse to obtain the component B for later use;
1500 parts by weight of Desmodur N3300 of the component A is weighed, the component A is added into the mixed component B, and the mixture is uniformly stirred to obtain the epoxy modified polyaspartic ester polyurea coating.
The modified polyaspartic acid ester polyurea coatings of examples 5 to 9 and the coatings of comparative examples 4 to 6 were coated on a tin plate having a thickness of 0.2mm by spraying or blade coating, and the tin plate was previously sprayed with a primer according to the requirements of the test indexes. The thickness of the coating is controlled to be 0.2 +/-0.02 mm, the film-making standard refers to JG/T172-2005, and the coating is cured and maintained for 7d at 25 +/-2 ℃ and then is subjected to performance test. Performance test reference standard: adhesion (cross-hatch method, GB/T9286-1998; pull-out adhesion, GB/T5210-2006), tensile strength (GB/T1701-1982), impact strength (GB/T732-1993), hardness (GB/T6739-2006), alkali resistance (240h, GB/T9274-1988), acid resistance (240h, GB/T9274-1988), machine oil resistance (240h, GB/T9274-1988), alternating cold and hot cycles (3 cycles, HG/T2884-1997), salt spray resistance (2000h, GB/T1771-2007), artificial aging resistance (4000h color difference, ASTM D4587-2005), low temperature bendability (-40 ℃, 1h, GB/T16777-2008). The results of the performance measurements are shown in table 3.
Table 3 test results of paint performances of examples 5 to 9 and comparative examples 4 to 6
As can be seen from the test data in Table 3, when the polyaspartic ester resins modified by the organosilicon units and the epoxy units are used in examples 5-9 and comparative examples 4-6, the adhesion, tensile strength and impact strength of the coating are increased, which indicates that the adhesion and mechanical properties of the modified coating with the substrate are improved; the impact property, the cold-hot alternate circulation and the low-temperature bending property are improved, which shows that the modified polyaspartic acid ester polyurea coating has excellent low-temperature flexibility; after 240 hours of acid and alkali resistance and engine oil resistance test, the modified polyurea coating is intact and has no change, which shows that the modified polyaspartic acid ester polyurea coating has good weather resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A modified polyaspartic acid ester polyurea coating comprises a component A and a component B, and is characterized in that according to parts by weight,
the component A comprises the following substances: isocyanates and/or isocyanate polymers;
the component B comprises the following substances: 20-75 parts of organic silicon and epoxy double modified polyaspartic acid ester resin, 5-35 parts of filler, 0.1-5 parts of pigment, 0.5-10 parts of auxiliary agent and 5-30 parts of solvent.
2. The modified polyaspartate polyurea coating of claim 1, wherein the isocyanate functionality is 2-3.
3. The modified polyaspartate polyurea coating of claim 1, wherein the silicone and epoxy dual modified polyaspartate resin is prepared from the following materials in parts by weight: 10-50 parts of polyamine, 5-35 parts of maleic ester, 5-20 parts of epoxy resin, 5-20 parts of silane coupling agent, 5-20 parts of polyisocyanate and 5-15 parts of organic solvent.
4. The modified polyaspartate polyurea coating of claim 3, wherein the preparation of the silicone and epoxy dual modified polyaspartate resin comprises the steps of:
(1) preparation of polyaspartic acid ester resin: adding polyamine into a reaction kettle filled with protective gas, stirring, heating to 65-80 ℃, dropwise adding maleic acid ester into the reaction kettle, reacting for 8-25 h, and cooling to obtain polyaspartic acid ester resin;
preparation of a prepolymer: adding a silane coupling agent and maleic ester into a reaction kettle filled with protective gas, stirring, heating to 55-75 ℃, and reacting for 10-15 hours; adding polyisocyanate, reacting for 1-4 h at the temperature of 60-70 ℃, cooling to obtain a prepolymer, and dissolving the prepolymer in an organic solvent for later use;
(2) adding the polyaspartic acid ester resin obtained in the step (1), epoxy resin and an organic solvent into a reaction kettle filled with protective gas, uniformly mixing, dropwise adding the prepolymer dissolved in the organic solvent obtained in the step (1) while stirring, heating to 65-80 ℃, reacting for 2-6 h, and cooling to obtain the organic silicon and epoxy double-modified polyaspartic acid ester resin.
5. The modified polyaspartate polyurea coating of claim 3, wherein the polyamine comprises any one of an aliphatic primary diamine or an amino terminated polyether; the maleate comprises any one of dimethyl maleate, diethyl maleate and dibutyl maleate; the epoxy resin comprises any one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and aliphatic glycidyl amine epoxy resin; the silane coupling agent is any one of amino functional group silane, methacryloxy functional group silane, vinyl triethoxysilane, vinyl trimethoxysilane, phenyl triethoxysilane and methyl triethoxysilane; the polyisocyanate comprises any one of IPDI trimer, HDI trimer and TDI trimer; the organic solvent is one or more of ester, ketone and benzene organic solvents.
6. The modified polyaspartate polyurea coating of claim 1, wherein the filler is one or more of calcium carbonate, kaolin, glass flakes, talc, silica powder, mica powder, and barium sulfate.
7. The modified polyaspartate polyurea coating of claim 1, wherein the pigment is one or more of titanium dioxide, iron black, carbon black, iron yellow or iron red.
8. The modified polyaspartate polyurea coating of claim 1, wherein the additive comprises, in parts by weight, 0.1 to 5 parts of a dispersant, 0.1 to 5 parts of an antifoaming agent, 0.1 to 5 parts of a leveling agent, and 0.1 to 5 parts of an anti-settling agent.
9. A process for the preparation of the modified polyaspartate polyurea coating according to any of claims 1 to 8, wherein A, B components are prepared separately,
preparation of the component A: adding isocyanate and/or polymer of the isocyanate into a container, and uniformly stirring to obtain a component A;
preparation of the component B: adding the organosilicon and epoxy double-modified polyaspartic acid ester resin into a container, respectively adding the filler, the pigment, the auxiliary agent and the solvent, and uniformly stirring and dispersing to obtain a component B;
and (2) mixing the component A and the component B according to the mass ratio of 1: 1-5, and uniformly stirring to obtain the modified polyaspartic acid ester polyurea coating.
10. The use of the modified polyaspartate polyurea coating according to any one of claims 1-8, wherein the modified polyaspartate polyurea coating is used as an anticorrosive coating for the surface of concrete, metal and composite materials to form an anticorrosive coating.
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