CN113045971A - Polyurea coating and preparation method thereof - Google Patents

Polyurea coating and preparation method thereof Download PDF

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CN113045971A
CN113045971A CN201911373395.9A CN201911373395A CN113045971A CN 113045971 A CN113045971 A CN 113045971A CN 201911373395 A CN201911373395 A CN 201911373395A CN 113045971 A CN113045971 A CN 113045971A
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powder filler
component
polyurea coating
triurea
coating
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王书元
叶卫
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Shenzhen Brilliant Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)

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  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to a polyurea coating comprising: polyaspartic acid esters; a triurea component; a ketone solvent, an ester solvent, an alcohol ether solvent, or a combination thereof; an alcohol solvent; non-graphite inorganic powder filler, metal powder filler or metal oxide powder filler with the fineness of more than 50 meshes; optionally a graphite powder filler with a fineness of 50 mesh or more; a diisocyanate trimer; and a molecular weight of 500-. The invention also provides a method for preparing the polyurea coating.

Description

Polyurea coating and preparation method thereof
Technical Field
The invention belongs to the field of polyurea coatings. The invention relates to a polyurea coating and a preparation method thereof, in particular to a slow polyurea coating with high solid content and low viscosity and a preparation method thereof.
Background
In recent years, with the increasing strictness of environmental regulations and the continuous improvement of coating processes, a high solid content paint (hereinafter, may also be simply referred to as a high solid content paint) has become a competitive paint and has been used in various fields such as automobile industry, ship industry, building industry, and the like. Currently available high solid content coatings can be divided into two broad categories: epoxy-based coatings and polyurethane-based coatings, of which polyurea coatings are considered to belong to the polyurethane-based coatings.
For high solid content paint, the paint viscosity is high due to the high solid content (usually more than 75%), and the paint cannot be coated by conventional coating processes such as spraying, rolling, brushing and the like. Taking the polyurea coating (also commonly referred to as polyurea elastomer in industry) commonly used at present as an example, although the polyurea coating belongs to a coating with lower viscosity in high solid content coating, the polyurea coating still needs expensive special equipment and severe construction conditions. Although the coating has the advantages of fast curing, low content of Volatile Organic Compounds (VOC), excellent protective performance and the like, improvement on the aspects of operation simplicity, construction cost and the like is still needed.
Therefore, the invention provides a novel polyurea coating and a preparation method thereof, and further solves some key technical problems existing in the field.
Disclosure of Invention
In a first aspect of the invention, there is provided a polyurea coating comprising or consisting of:
Figure BDA0002340295900000021
wherein the polyaspartic acid ester has a structure represented by the following formula 1:
Figure BDA0002340295900000022
in the general formula 1, R is C1-4Straight or branched chain alkyl, X is C1-15An alkylene group;
the triurea component is selected from one or more of methyl octadecamethylene tricarbamate triurea, ethyl octadecamethylene tricarbamate triurea, propyl octadecamethylene tricarbamate triurea, butyl octadecamethylene tricarbamate triurea, silicon octadecamethylene tricarbamate triurea and the combination thereof;
the diisocyanate trimer has a structure represented by the following general formula 2:
Figure BDA0002340295900000031
in the general formula 2, R is C3-10A linear alkylene group,
wherein the weight% is based on the weight of the polyurea coating, and the content of the solid component in the polyurea coating is 80 weight% or more.
In one embodiment, in formula 1, R is ethyl and X is a structure represented by the following formula 3:
Figure BDA0002340295900000032
in one embodiment, in formula 2, R is hexylene.
In another embodiment, the alcoholic solvent is ethanol, methylal or a combination thereof, and when methylal is present, the methylal content is 2 to 8% by weight. In yet another embodiment, the ketone solvent is acetone, the ester solvent is ethyl acetate, and the alcohol ether solvent is dipropylene glycol dimethyl ether.
In one embodiment, the triurea component is a mixture of 1-15 wt.% methyl octadecamethylene tricarbamate triurea and 1-15 wt.% silicon octadecamethylene tricarbamate triurea. In another embodiment, the polyurethane resin having a molecular weight of 500-1000 is a methyl polyurethane. In yet another embodiment, the polyurethane resin having a molecular weight of 500-1000 is prepared from an isocyanate having a molecular weight of 500-1000 and methanol by the following process: and (2) uniformly mixing 15 parts of methanol with the purity of more than 99% and 60-75 parts of hexamethylene diisocyanate trimer for reacting for 6-8 days at normal temperature and pressure.
In one embodiment, the non-graphitic inorganic powder filler, metal powder filler, or metal oxide powder filler having a fineness of 50 mesh or more is a metal of 50-3000 mesh or nanometers, a metal oxide powder filler having a fineness of 50-3000 mesh or nanometers, a non-graphitic inorganic powder filler having a fineness of 50-3000 mesh or nanometers, or a combination thereof, and the graphite powder filler having a fineness of 50 mesh or more is a graphite powder filler of 50-3000 mesh or nanometers. In another embodiment, the metal powder filler or metal oxide powder filler is present in an amount of 10 to 80 weight percent, the graphite powder filler is present in an amount of 0 to 30 weight percent, and the non-graphite inorganic powder filler is present in an amount of 0 to 50 weight percent.
In one embodiment, the metal powder filler or metal oxide powder filler is zinc powder, iron oxide powder, copper oxide powder, aluminum powder, or a combination thereof having a fineness of 50-3000 mesh or nanometers. In another embodiment, the graphite powder filler is microcrystalline graphite, graphene, or a combination thereof. In yet another embodiment, the graphite powder filler has a carbon content of 99.9% or greater. In one embodiment, the non-graphitic inorganic powder filler is a silica-based powder, an inorganic pigment, calcium carbonate, talc, kaolin, or a combination thereof. In another embodiment, the powder filler is present in an amount of 75 to 95 weight percent based on the weight of the dried polyurea coating after the polyurea coating is completely dried.
In a second aspect of the invention, there is provided a method of preparing a polyurea coating described herein, comprising: uniformly mixing a diisocyanate trimer represented by formula 2 with a ketone solvent, an ester solvent, an alcohol ether solvent or a combination thereof, thereby obtaining a component A; uniformly mixing an alcohol solvent and an optional ketone solvent, an ester solvent, an alcohol ether solvent and a triurea component, adding polyaspartic acid ester represented by a general formula 1 and an optional polyurethane with a molecular weight of 500-1000, uniformly mixing, then adding a non-graphite inorganic powder filler, a metal powder filler or a metal oxide powder filler or a combination thereof with a fineness of more than 50 meshes, and uniformly mixing to obtain a component B; mixing the component A with the component B, thereby obtaining the polyurea coating.
In another embodiment, a method of making a polyurea coating described herein comprises: mixing hexamethylene diisocyanate trimer and hydroxy polyester to obtain diisocyanate trimer represented by a general formula 2 as a chain extender, adding any one or a mixture of three of acetone, ethyl acetate and dipropylene glycol dimethyl ether in any proportion, and uniformly mixing to obtain a component A; mixing the methyl octadecamethylenetricarbamate triurea, the silicon octadecamethylenetricarbamate triurea and the methylal uniformly, adding polyaspartic acid ester having a structure represented by general formula 1, wherein R is ethyl and X is represented by formula 3, and mixing uniformly, and then adding non-graphitic inorganic powder filler, metal powder filler or metal oxide powder filler having a fineness of 50-3000 mesh or nanometer or a combination thereof and mixing uniformly, thereby obtaining component b; mixing the component A with the component B, thereby obtaining the polyurea coating.
In yet another embodiment, a method of preparing a polyurea coating described herein comprises: uniformly mixing a diisocyanate trimer represented by formula 2 with a ketone solvent, an ester solvent, an alcohol ether solvent or a combination thereof, thereby obtaining a component A; uniformly mixing an alcohol solvent and an optional ketone solvent, an ester solvent, an alcohol ether solvent and a triurea component, adding polyaspartic acid ester represented by a general formula 1 and an optional polyurethane with a molecular weight of 500-1000, uniformly mixing, then adding a non-graphite inorganic powder filler, a metal powder filler or a metal oxide powder filler or a combination thereof with a fineness of more than 50 meshes, simultaneously or subsequently adding a graphite powder filler with a fineness of more than 50 meshes, and uniformly mixing to obtain a component B; mixing the component A with the component B, thereby obtaining the polyurea coating.
Detailed Description
Hereinafter, the present invention will be further illustrated according to specific embodiments. However, the specific embodiments are set forth for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those of skill in the art that a particular feature presented in any of the embodiments below may be used in any other embodiment or may be combined with other particular features in other embodiments without departing from the spirit of the invention.
General definitions
The technical terms given herein may be interpreted using the definitions set out below, and, if not explicitly stated, may also be interpreted using the ordinary meaning in the art. The definitions given herein control when the definitions set forth below are contrary to the ordinary meaning in the art.
As used herein, a high solids coating is defined as: the solid component content in the coating is more than 75 wt%.
As used herein, a low viscosity coating is defined as: the viscosity of the coating is measured at 25. + -. 0.2 ℃ using a paint-4 viscometer according to the measurement method specified in GB1723-79, and when the viscosity reaches 20-30 seconds, the coating can be regarded as a low viscosity coating. In short, the viscosity of the coating can be measured by the following method: during measurement, the viscometer is adjusted to be in a horizontal state at the temperature of 25 +/-0.2 ℃, a 150ml beaker is placed under the viscometer, a ball valve is used for blocking a leakage nozzle hole, the coating is poured into the viscometer, then the coating flows out, a stopwatch is started to count time at the same time until the flowing thread of the coating is interrupted, the timing is stopped immediately, the time is the conditional viscosity of the glue solution, the measurement is repeated three times, and the error is not more than 3 percent of the average value.
As used herein, polyurea coating refers to a coating having a polyamine content greater than 80% of the main chain of the film-forming resin of the coating, wherein the main chain of the resin is a urea group-containing compound.
As used herein, a slow polyurea coating refers to a coating that can be applied for a time longer than 1 hour at ambient temperature (25 ± 0.2 ℃). In this context, curing of the polyurea coating is predominantly effected by the polyamine crosslinker by crosslinking reaction with the isocyanate chain extender.
As used herein, alkyl refers to a monovalent group of a saturated aliphatic hydrocarbon that is straight, branched, or cyclic, or a combination thereof, while alkylene refers to a divalent group of a saturated aliphatic hydrocarbon that is straight, branched, or cyclic, or a combination thereof. Carbon number C used in modification of alkyl or alkylene1-15It is to be construed that the group contains 1 to 15 carbon atoms, or any number in the range of 1 to 15 carbon atoms, for example 3, 5, 10 carbon atoms. Other carbon number (e.g. C)1-4) And may be interpreted identically. Examples of alkyl groups include, but are not limited to: methyl, methyl,Ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl and the like.
In this context, the temperature is not particularly limited, and all means that the operation is carried out at ambient temperature (25. + -. 0.2 ℃ C.).
Polyurea coating
In one embodiment, the polyurea coating may comprise or consist of the following components:
Figure BDA0002340295900000061
Figure BDA0002340295900000071
wherein the weight% is based on the weight of the polyurea coating, and the content of the solid component in the polyurea coating is 80 weight% or more.
In this regard, the solid component in the polyurea coating means a component other than the solvent and not a component which must be solid at the time of formulation, and the solid component includes polyaspartic acid ester, triurea component, powder filler, diisocyanate trimer and polyurethane resin having a molecular weight of 500-.
In one embodiment, the polyaspartic acid ester has a structure represented by the following formula 1:
Figure BDA0002340295900000072
in the general formula 1, R is C1-4Straight-chain or branched alkyl, e.g. methyl, ethyl, propyl, n-butyl or tert-butyl, X is C1-15An alkylene group. Here, X may be a linear alkyl group, a branched alkyl group, a cyclic alkyl group, or a combination thereof, of which the total carbon number is 15 or less.
In another embodiment, in formula 1, R is ethyl and X is a structure represented by the following formula 3:
Figure BDA0002340295900000073
in yet another embodiment, in formula 2, R is hexylene.
In this regard, the polyaspartic esters used herein can be synthesized directly by synthetic methods known in the art, or can be commercially available, such as F-520 polyaspartic ester from Shenzhen Feiyang industries, Ltd, NH 1520 from Germany Bayer, and the like. The polyaspartic acid ester used herein has high symmetry and can generate inclusion compound during formulation, thereby enabling to reduce viscosity and achieve high solid content. In one embodiment, the polyaspartic acid ester may be present in an amount of 5 to 35 weight percent, such as 10 weight percent, 15 weight percent, 20 weight percent, 25 weight percent, or 30 weight percent.
In one embodiment, the triurea component may be selected from one or more of the group consisting of methyl octadecamethylene tricarbamate triurea, ethyl octadecamethylene tricarbamate triurea, propyl octadecamethylene tricarbamate triurea, butyl octadecamethylene tricarbamate triurea, silicon octadecamethylene tricarbamate triurea, and combinations thereof. In another embodiment, the triurea component may be present in an amount of 1 to 15% by weight, such as 2%, 3%, 5%, 8%, 10%, 12% or 14% by weight.
In one embodiment, the triurea component may be a mixture of methyl octadecamethylene tricarbamate triurea and silicon octadecamethylene tricarbamate triurea. In another embodiment, the triurea component is a mixture of 1-15% by weight of methyl octadecamethylene tricarbamate triurea and 1-15% by weight of silicon octadecamethylene tricarbamate triurea. For example, the triurea component can be a mixture of 1.41 weight percent methyl octadecamethylene tricarbamate triurea and 3.44 weight percent silicon octadecamethylene tricarbamate triurea.
In one embodiment, the diisocyanate trimer has a structure represented by the following formula 2:
Figure BDA0002340295900000081
in the general formula 2, R is C3-10Straight chain alkylene groups such as propylene, butylene, hexylene, and the like.
In another embodiment, the diisocyanate trimer may have a structure represented by formula 2 above, wherein R is hexamethylene, i.e., the diisocyanate trimer is HDI trimer (also referred to as hexamethylene diisocyanate trimer). In one embodiment, the diisocyanate trimer content may be 5 to 35% by weight, such as 10%, 15%, 20%, 25% or 30% by weight.
In one embodiment, the alcoholic solvent is ethanol, methylal derived from methanol, or a combination thereof, and when methylal is present, methylal is present in an amount of 2 to 8% by weight, such as 3%, 4%, 5%, 6%, or 7%. In yet another embodiment, the ketone solvent is acetone, the ester solvent is ethyl acetate, and the alcohol ether solvent is dipropylene glycol dimethyl ether. For this purpose, if the odor requirements of the application process are high, ethanol can be used instead of the ketone solvents and ester solvents mentioned above. In this embodiment, the ethanol is added in its entirety to the second component described below to avoid reaction of the ethanol with the HDI trimer. In this case, the component A can only be pure HDI trimer, and the viscosity of the component A is high, so that the component A is not easy to flow completely in a container. When in use, the component B can be poured into the component A container to ensure the accuracy of the paint proportioning.
In one embodiment, the polyurethane resin having a molecular weight of 500-1000 is a methyl polyurethane. In another embodiment, the polyurethane with molecular weight 500-1000 is prepared from isocyanate with molecular weight 500-1000 and methanol by the following process: and (2) uniformly mixing 15 parts of methanol with the purity of more than 99% and 60-75 parts of hexamethylene diisocyanate trimer for reacting for 6-8 days at normal temperature and pressure.
In one embodiment, the non-graphitic inorganic powder filler, metal powder filler, or metal oxide powder filler having a fineness of 50 mesh or greater is a metal powder filler having a fineness of 50-3000 mesh or nanometers, a metal oxide powder filler having a fineness of 50-3000 mesh or nanometers, a non-graphitic inorganic powder filler having a fineness of 50-3000 mesh or nanometers, or a combination thereof. In another embodiment, the metal powder filler or metal oxide powder filler is zinc powder, iron oxide powder, copper oxide powder, aluminum powder, or a combination thereof having a fineness of 50-3000 mesh or nanometers. For example, the non-graphitic inorganic powder filler, metal powder filler or metal oxide powder filler may be a metal powder having a fineness of 500-1250 mesh, such as a zinc powder having a fineness of 500-800 mesh, an iron oxide powder, a copper oxide powder, an aluminum powder or a combination thereof. With such powder fillers, high solids content (i.e., high packing ratio) can be achieved while reducing the production cost of the polyurea coating without affecting the basic coating properties of the polyurea coating.
In one embodiment, the graphite powder filler having a fineness of 50 mesh or more is a graphite powder filler of 50 to 3000 mesh or nano-scale. In another embodiment, the graphite powder filler is microcrystalline graphite, graphene, or a combination thereof. In yet another embodiment, the graphite powder filler has a carbon content of 99.9% or greater. The polyurea coating is added with a proper amount of graphite powder, so that the coating is suitable for cold spraying and has outstanding salt spray resistance.
In one embodiment, the non-graphitic inorganic powder filler is a silica-based powder, an inorganic pigment, calcium carbonate, talc, kaolin, or a combination thereof. In another embodiment, the metal powder filler is present in an amount of 10 to 80 weight percent, the graphite powder filler is present in an amount of 0 to 30 weight percent, and the non-graphite inorganic powder filler is present in an amount of 0 to 50 weight percent. In this case, the total content of powder filler can be greater than 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, or even greater than 70 wt.% or 75 wt.%. In yet another embodiment, the powder filler is present in an amount of 75 to 95 weight percent based on the weight of the dried polyurea coating after the polyurea coating is completely dried.
In the polyurea coatings described hereinabove, the polyamine content in the main chain of the coating film-forming resin is greater than 86.58%, thus complying with the relevant regulations for polyurea coatings, for example, the classification and definition made by the american polyurea development society for polyurea and polyurethane coatings: when the polyamine content in the system is more than 80%, the material is called polyurea coating; when the content of the polyol in the system is more than 80 percent, the material is called polyurethane coating; and when the content of polyamine and polyalcohol in the system is between the two, the materials are collectively called polyurea/polyurethane hybrid or mixture.
The polyurea coatings provided herein can still achieve a viscosity of 20-30 seconds (measured as described above using a coat-4 viscometer) at high solids content. In practice, the polyurea coatings provided herein have a coating run time of greater than 1 hour (typically 1-3 hours), such as greater than 5 hours if diluted with a diluent (e.g., diluted at a rate of plus one-fifteenth of the diluent per hour), while the coating effect remains unchanged. Thus, it can be seen that the polyurea coating provided herein is a high solids low viscosity slow polyurea coating.
Based on these properties, the polyurea coatings provided herein can be applied using conventional coating equipment, as required by conventional coating techniques (e.g., using spray, roller, brush, etc.), and in actual testing, have been used to prepare polyurea zinc-rich basecoats and polyurea cold spray zinc coatings, and have achieved and exceeded performance specifications for other zinc-rich basecoats and cold spray zinc coatings. In addition, because the polyurea coating provided by the invention has relatively long curing time and low viscosity, the polyurea coating can fully wet a base surface, destructive stress does not exist in an interface and the coating, and the phenomena of bubbling, pinholes, shrinkage cracking and the like can be avoided. Furthermore, the polyurea coatings provided herein can produce thin coatings with dry film thicknesses of only 15-20 microns, whereas typical high solids coatings typically have dry film thicknesses of greater than 100 microns, with only a few capable of achieving dry film thicknesses on the order of 80 microns.
Process for preparing polyurea coatings
In one embodiment, a method of preparing a polyurea coating described herein comprises: uniformly mixing diisocyanate trimer represented by a general formula 2 with a ketone solvent, an ester solvent, an alcohol ether solvent or a combination thereof (namely, the mixed system is clear after standing, the same applies below), thereby obtaining a component A; uniformly mixing an alcohol solvent and an optional ketone solvent, an ester solvent, an alcohol ether solvent and a triurea component, adding polyaspartic acid ester represented by a general formula 1 and an optional polyurethane with a molecular weight of 500-1000, uniformly mixing, then adding a non-graphite inorganic powder filler, a metal powder filler or a metal oxide powder filler or a combination thereof with a fineness of more than 50 meshes, and uniformly mixing to obtain a component B; mixing the A component with the B component (for example, in a weight ratio of 1: 7-10), thereby obtaining the polyurea coating.
In this embodiment, the liquid component must be mixed well and then the powder filler is added when preparing the component B. If various liquid components which are not mixed are added into the powder filler, the prepared component B is easy to generate the phenomenon of precipitation. In addition, the prepared component B is preferably used within 15 days, and the component B can generate solid precipitation after more than 15 days, so that the component B needs to be stirred uniformly again for use, but does not need to be prepared again. For this, the storage life of the component A is one year, and the storage life of the component B is six months.
In one embodiment, the method of making comprises: mixing hexamethylene diisocyanate trimer and hydroxyl polyester (for example, molecular weight 2000) to obtain diisocyanate trimer represented by general formula 2 as a chain extender, adding any one or a mixture of three of acetone, ethyl acetate and dipropylene glycol dimethyl ether at an arbitrary ratio thereto, and uniformly mixing to obtain a component A; mixing the methyl octadecamethylenetricarbamate triurea, the silicon octadecamethylenetricarbamate triurea and the methylal uniformly, adding polyaspartic acid ester having a structure represented by general formula 1, wherein R is ethyl and X is represented by formula 3, and mixing uniformly, and then adding non-graphitic inorganic powder filler, metal powder filler or metal oxide powder filler having a fineness of 50-3000 mesh or nanometer or a combination thereof and mixing uniformly, thereby obtaining component b; mixing the component A with the component B, thereby obtaining the polyurea coating.
In one embodiment, a method of preparing a polyurea coating described herein comprises: uniformly mixing a diisocyanate trimer represented by formula 2 with a ketone solvent, an ester solvent, an alcohol ether solvent or a combination thereof, thereby obtaining a component A; uniformly mixing an alcohol solvent and an optional ketone solvent, an ester solvent, an alcohol ether solvent and a triurea component, adding polyaspartic acid ester represented by a general formula 1 and an optional polyurethane with a molecular weight of 500-1000, uniformly mixing, then adding a non-graphite inorganic powder filler, a metal powder filler or a metal oxide powder filler or a combination thereof with a fineness of more than 50 meshes, simultaneously or subsequently adding a graphite powder filler with a fineness of more than 50 meshes, and uniformly mixing to obtain a component B; mixing the component A with the component B, thereby obtaining the polyurea coating.
In the preparation method provided by the invention, the gel point of the coating is controlled by regulating and controlling the concentration of the chain extender and the concentration of isocyanate through high filling in the polyurea coating, so that the operation time of the coating is increased. In addition, there is a need to heavily consider and select resins that have good compatibility with polyurea coating systems, low viscosity, allow the addition of a large amount of inorganic fillers in polyurea coating systems, and ensure stable polyurea coating properties, including, for example, octadecyltrimethylarbamate triurea, and the like. Preferably, the resin is a mixture of methyl octadecamethylene tricarbamate triurea and silicon octadecamethylene tricarbamate triurea.
Use and use of polyurea coatings
The polyurea coating provided by the invention has low viscosity and long curing time, so that the coating can be carried out without special polyurea coating equipment. For example, the components A and B can be mixed in proportion and uniformly stirred at room temperature (stirring for 5-8 minutes by a stirrer with the rotating speed of 300-500 rpm is recommended), and then the spraying and coating can be carried out by using conventional air spraying equipment under the condition of the gas pressure of 3-8 kg/square centimeter; and (3) carrying out spraying and coating by using general airless spraying equipment under the condition of gas pressure of 5-12 kg/square centimeter.
The polyurea coating provided by the invention has good environmental protection performance, simple and convenient construction and far better physical and chemical properties than the prior water-based coating, and can be used in the building industry, the metal protection industry and the furniture industry. Additionally, the polyurea coatings provided herein solve the problem of polyurea protective coatings having no zinc-rich products when zinc powder is used as the inorganic filler.
Examples
Hereinafter, the present invention is described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto. The reagents used in the examples are commercially available, in particular:
the polyaspartate is F-520, the relative molecular weight is 580, and the NH equivalent is 290 g/mol; the methylal is chemically pure; the methyl octadecamethylene tricarbamate triurea and the silicon octadecamethylene tricarbamate triurea are self-made products; the inorganic filler is 500-mesh zinc powder purchased from New Weiling Metal New materials GmbH; HDI trimer was purchased from Wanhua corporation, type HT-100; acetone is a commercially available technical grade chemically pure ketone.
Hereinafter, "parts" means parts by weight unless otherwise specified.
Example 1
28.392 parts of HT-100 and 43 parts of acetone are mixed together at room temperature, and are fully and uniformly stirred by a dispersion stirrer (the mixed system is clear after standing), so that the component A of the polyurea coating is prepared and is sealed for storage.
An ethanol solution containing 10.716 parts of methylal and 9.284 parts of octadecyl methylene tricarbamate triurea and 22.608 parts of octadecyl methylene tricarbamate triurea ethanol solution are uniformly mixed, 44 parts of polyaspartic acid ester F-520 are added, 500 parts of 500-mesh zinc powder is added after uniform mixing, and the mixture is fully and uniformly stirred by a dispersion stirrer, so that a component B of the polyurea coating is prepared and is stored in a sealed manner.
9.284 parts of an ethanolic solution of methyl octadecamethylenetricarbamate triurea: 52% by weight of methyl octadecamethylenetricarbamate triurea; 48% by weight of ethanol. 22.608 parts of ethanol solution of octadecyl methylene triaminosilicon formate triurea is as follows: 63% of octadecyl trimethyl carbamate triurea and 37% of ethanol.
Before coating, the coating comprises the following components: the component B is 1: 8.22, and stirring uniformly to obtain the coating. The formulation of the polyurea coating of example 1 is shown in table 1 below.
Table 1: formulation of the polyurea coating of example 1
Figure BDA0002340295900000131
Figure BDA0002340295900000141
Comparative example 1
A polyurea coating was prepared in the same manner as in example 1, but using the additional amine chain extender, dimethylthiotoluenediamine (DMTDA), having a molecular weight of 214.34 and an amine equivalent weight of 107.17, as specified in Table 2 below:
table 2: formulation of the polyurea coating of comparative example 1
Figure BDA0002340295900000142
The polyurea coating in this comparative example had components A and B mixed for less than three minutes, and the coating was hot and started to gel, and could not be used. The polyurea coating can be sprayed only by a double-component high-pressure airless spraying device.
Example 2
At room temperature, 132 parts of HDI trimer prepolymer (chain extender), 58 parts of self-made polyurethane with molecular weight of 500-1000 and 62 parts of methylal are mixed together, and are fully and uniformly stirred by a dispersion stirrer (at the moment, the mixed system is clear after standing), so that the component A of the polyurea coating is prepared and is stored in a sealed manner.
Uniformly mixing 45 parts of methylal, 24 parts of octadecamethylene tricarbamate triurea and 115 parts of dipropylene glycol dimethyl ether, adding 132 parts of polyaspartic acid ester F-520, further uniformly mixing, adding 1500 parts of 500-mesh zinc powder and 38 parts of microcrystalline graphite, fully and uniformly stirring by using a dispersion stirrer to obtain a component B of the polyurea coating, and sealing and storing.
Before coating, the coating comprises the following components: the component B is mixed according to the proportion of 252:1854, and is stirred evenly, thus being coated for use. The formulation of the polyurea coating of example 2 is shown in table 3 below.
Table 3: formulation of polyurea coating of example 2
Figure BDA0002340295900000151
The polyurea coating of this embodiment can be used as a cold spray zinc coating product in the zinc rich coating type, which can also be referred to as a polyurea cold spray zinc coating. The polyurea cold-spraying zinc coating has the characteristics of enhancing the cathodic protection performance of zinc and improving the hardness of a zinc-rich coating, and is particularly remarkable in the aspect of enhancing the salt spray resistance of the cathodic protection performance of zinc.
The salt spray resistance of the polyurea cold spray zinc coating of example 2 is compared to that of a conventional cold spray zinc coating as follows:
table 4: the salt spray resistance of the polyurea cold spray zinc coating is compared with that of the conventional cold spray zinc coating
Figure BDA0002340295900000161
Example 3
Under the same conditions as in example 2, the polyurea coating of example 3 was prepared, the components of which are shown in table 5 below.
Table 5: formulation of polyurea coating of example 3
Figure BDA0002340295900000162
Figure BDA0002340295900000171
Example 4
At room temperature, 132 parts of HDI trimer prepolymer (chain extender), 58 parts of self-made polyurethane with molecular weight of 500-1000 and 62 parts of methylal are mixed together, and are fully and uniformly stirred by a dispersion stirrer (at the moment, the mixed system is clear after standing), so that the component A of the polyurea coating is prepared and is stored in a sealed manner.
Uniformly mixing 45 parts of methylal and 24 parts of octadecamethylene tricarbamate triurea, adding 132 parts of polyaspartic acid ester F-520, further uniformly mixing, adding 1500 parts of 500-mesh zinc powder and 38 parts of 1200-mesh fumed silica, fully and uniformly stirring by using a dispersion stirrer to obtain the component B of the polyurea coating, and sealing and storing.
Before coating, the coating comprises the following components: the component B is mixed according to the proportion of 252:1854, and is stirred evenly, thus being coated for use. The formulation of the polyurea coating of example 3 is shown in table 6 below.
Table 6: formulation of polyurea coating of example 4
Figure BDA0002340295900000172
Example 5
At room temperature, 132 parts of HDI trimer prepolymer (chain extender), 58 parts of self-made polyurethane with molecular weight of 500-1000 and 62 parts of methylal are mixed together, and are fully and uniformly stirred by a dispersion stirrer (at the moment, the mixed system is clear after standing), so that the component A of the polyurea coating is prepared and is stored in a sealed manner.
Uniformly mixing 45 parts of methylal and 24 parts of octadecamethylene tricarbamate triurea, adding 132 parts of polyaspartic acid ester F-520, further uniformly mixing, adding 1500 parts of 120-mesh iron oxide red powder and 38 parts of 1200-mesh fumed silica, fully and uniformly stirring by using a dispersion stirrer, thus preparing the component B of the polyurea coating, and sealing and storing.
Before coating, the coating comprises the following components: the component B is mixed according to the proportion of 252:1854, and is stirred evenly, thus being coated for use. The formulation of the polyurea coating of example 4 is shown in table 7 below.
Table 7: formulation of polyurea coating of example 5
Figure BDA0002340295900000181
Example 6
At room temperature, 141 parts of HT-100 and 52 parts of dipropylene glycol dibenzoate are mixed together and fully and uniformly stirred by a dispersion stirrer (at the moment, the mixed system is clear after standing), so that the component A of the polyurea coating is prepared and sealed for storage.
Uniformly mixing 20 parts of ethyl acetate, 16 parts of ethanol and 8 parts of octadecylidene triscarbamic acid silicone ester triurea, adding 141 parts of polyaspartic acid ester F-520, further uniformly mixing, adding 76 parts of 1200-mesh titanium dioxide, fully and uniformly stirring by using a dispersion mixer, thus preparing the component B of the polyurea coating, and sealing and storing.
Before coating, the coating comprises the following components: and mixing the component B142: 261, and uniformly stirring to obtain the coating. The formulation of the polyurea coating of example 5 is shown in table 8 below.
Table 8: formulation of polyurea coating of example 6
Figure BDA0002340295900000191
Example 7
At room temperature, 150 parts of HT-100 and 38 parts of dipropylene glycol dibenzoate are mixed together, and fully and uniformly stirred by a dispersion stirrer (at the moment, the mixed system is clear after standing), so that the component A of the polyurea coating is prepared and sealed for storage.
Uniformly mixing 20 parts of ethyl acetate, 16 parts of ethanol and 8 parts of octadecylidene triscarbamic acid silicone ester triurea, adding 120 parts of polyaspartic acid ester F-520, further uniformly mixing, adding 76 parts of 1200-mesh titanium dioxide, fully and uniformly stirring by using a dispersion mixer, thus preparing the component B of the polyurea coating, and sealing and storing.
Before coating, the coating comprises the following components: and mixing the component B188 to 240, and stirring uniformly to obtain the coating. The formulation of the polyurea coating of example 6 is shown in table 9 below.
Table 9: formulation of polyurea coating of example 7
Figure BDA0002340295900000201
Example 8
At room temperature, 121 parts of HT-100 and 480 parts of dipropylene glycol dibenzoate are mixed together, and fully and uniformly stirred by a dispersion stirrer (at the moment, the mixed system is clear after standing), so that the component A of the polyurea coating is prepared and sealed for storage.
Uniformly mixing 180 parts of dipropylene glycol dimethyl ether, 62 parts of ethanol and 5 parts of octadecylidene triscarbamic acid silicone ester triurea, adding 121 parts of polyaspartic acid ester F-520, further uniformly mixing, adding 492 parts of 1200-mesh titanium dioxide, then adding 1080 parts of 800-mesh glass powder, fully and uniformly grinding by using a three-roll grinder, thus preparing the component B of the polyurea coating, and sealing and storing.
Before coating, the coating comprises the following components: and (3) mixing the component B601: 1940, and uniformly stirring to obtain the coating. The formulation of the polyurea coating of example 7 is shown in table 10 below.
Table 10: formulation of polyurea coating of example 8
Figure BDA0002340295900000211
Experimental example 1
The following table shows the test results of the polyurea coatings obtained in example 1 and comparative example 1.
Table 11: parameters of polyurea coating
Figure BDA0002340295900000212
Therefore, the polyurea coating provided by the invention has the characteristics of high solid content, low viscosity and long curing time, so that the polyurea coating can be coated by using a conventional process, the construction cost of polyurea is greatly reduced, and the coating process is simplified. The polyurea coating provided by the invention has the advantages that due to the high filling ratio of the inorganic filler, compared with the same type of products, the production and construction cost is greatly reduced, the production process is more environment-friendly, and no three wastes are discharged.
In addition, the polyurea coating provided by the invention passes the detection and verification of the United states KTA laboratory, can be used for protecting containers, and has been subjected to multiple spraying experiments in centralized production sites in the south, so that the process use requirements of a container coating spraying production line are completely met.
While specific embodiments of the present invention have been described above with reference to specific examples, it will be appreciated by those skilled in the art that various modifications and changes may be made thereto without departing from the scope and spirit of the invention.

Claims (10)

1. A polyurea coating, comprising:
Figure FDA0002340295890000011
wherein the polyaspartic acid ester has a structure represented by the following formula 1:
Figure FDA0002340295890000012
in the general formula 1, R is C1-4Straight or branched chain alkyl, X is C1-15An alkylene group;
the triurea component is selected from one or more of methyl octadecamethylene tricarbamate triurea, ethyl octadecamethylene tricarbamate triurea, propyl octadecamethylene tricarbamate triurea, butyl octadecamethylene tricarbamate triurea, silicon octadecamethylene tricarbamate triurea and the combination thereof;
the diisocyanate trimer has a structure represented by the following general formula 2:
Figure FDA0002340295890000021
in the general formula 2, R is C3-10A linear alkylene group,
wherein the weight% is based on the weight of the polyurea coating, and the content of the solid component in the polyurea coating is 80 weight% or more.
2. The polyurea coating of claim 1, wherein in formula 1, R is ethyl and X is a structure represented by the following formula 3:
Figure FDA0002340295890000022
and in formula 2, R is hexylene.
3. The polyurea coating of claim 1, wherein the alcoholic solvent is ethanol, methylal, or a combination thereof, and when methylal is present, the methylal content is 2-8 wt%; and/or
The ketone solvent is acetone, the ester solvent is ethyl acetate, and the alcohol ether solvent is dipropylene glycol dimethyl ether.
4. The polyurea coating of claim 1, wherein the triurea component is a mixture of 1-15% by weight of octadecylidene tricarbamate triurea and 1-15% by weight of octadecylidene tricarbamate triurea; and/or
The polyurethane resin with the molecular weight of 500-1000 is methyl polyurethane, and is prepared by the following steps of reacting isocyanate with the molecular weight of 500-1000 and methanol:
and (2) uniformly mixing 15 parts of methanol with the purity of more than 99% and 60-75 parts of hexamethylene diisocyanate trimer for reacting for 6-8 days at normal temperature and pressure.
5. The polyurea coating of claim 1, wherein the non-graphitic inorganic powder filler, metal powder filler, or metal oxide powder filler having a fineness of 50 mesh or more is a metal powder filler having a fineness of 50-3000 mesh or nanometers, a metal oxide powder filler having a fineness of 50-3000 mesh or nanometers, a non-graphitic inorganic powder filler having a fineness of 50-3000 mesh or nanometers, or a combination thereof, and the graphite powder filler having a fineness of 50 mesh or more is a graphite powder filler having a fineness of 50-3000 mesh or nanometers;
the content of the metal or metal oxide powder filler is 10-80 wt%, the content of the graphite powder filler is 0-30 wt%, and the content of the non-graphite inorganic powder filler is 0-50 wt%.
6. The polyurea coating of claim 5, wherein the metal or metal oxide powder filler is zinc powder, iron oxide powder, copper oxide powder, aluminum powder, or a combination thereof, having a fineness of 50-3000 mesh or nanometers; and/or
The graphite powder filler is microcrystalline graphite, graphene or a combination thereof, and preferably, the carbon content of the graphite powder filler is more than 99.9%; and/or
The non-graphitic inorganic powder filler is a silica-based powder, an inorganic pigment, calcium carbonate, talc, kaolin, or a combination thereof.
7. The polyurea coating of any one of claims 1 to 6, wherein the powder filler is present in an amount of 75-95 wt% based on the weight of the dried polyurea coating after the polyurea coating is completely dried.
8. A method of preparing the polyurea coating of any one of claims 1 to 7, comprising:
uniformly mixing a diisocyanate trimer represented by formula 2 with a ketone solvent, an ester solvent, an alcohol ether solvent or a combination thereof, thereby obtaining a component A;
uniformly mixing an alcohol solvent and an optional ketone solvent, an ester solvent, an alcohol ether solvent and a triurea component, adding polyaspartic acid ester represented by a general formula 1 and an optional polyurethane with a molecular weight of 500-1000, uniformly mixing, then adding a non-graphite inorganic powder filler, a metal powder filler or a metal oxide powder filler or a combination thereof with a fineness of more than 50 meshes, and uniformly mixing to obtain a component B;
mixing the component A with the component B, thereby obtaining the polyurea coating.
9. The method of claim 8, comprising:
mixing hexamethylene diisocyanate trimer and hydroxy polyester to obtain diisocyanate trimer represented by a general formula 2 as a chain extender, adding any one or a mixture of three of acetone, ethyl acetate and dipropylene glycol dimethyl ether in any proportion, and uniformly mixing to obtain a component A;
mixing the methyl octadecamethylenetricarbamate triurea, the silicon octadecamethylenetricarbamate triurea and the methylal uniformly, adding polyaspartic acid ester having a structure represented by general formula 1, wherein R is ethyl and X is represented by formula 3, and mixing uniformly, and then adding non-graphitic inorganic powder filler, metal powder filler or metal oxide powder filler having a fineness of 50-3000 mesh or nanometer or a combination thereof and mixing uniformly, thereby obtaining component b;
mixing the component A with the component B, thereby obtaining the polyurea coating.
10. A method of preparing the polyurea coating of any one of claims 1 to 7, comprising:
uniformly mixing a diisocyanate trimer represented by formula 2 with a ketone solvent, an ester solvent, an alcohol ether solvent or a combination thereof, thereby obtaining a component A;
uniformly mixing an alcohol solvent and an optional ketone solvent, an ester solvent, an alcohol ether solvent and a triurea component, adding polyaspartic acid ester represented by a general formula 1 and an optional polyurethane with a molecular weight of 500-1000, uniformly mixing, then adding a non-graphite inorganic powder filler, a metal powder filler or a metal oxide powder filler or a combination thereof with a fineness of more than 50 meshes, simultaneously or subsequently adding a graphite powder filler with a fineness of more than 50 meshes, and uniformly mixing to obtain a component B;
mixing the component A with the component B, thereby obtaining the polyurea coating.
CN201911373395.9A 2019-12-27 2019-12-27 Polyurea coating and preparation method thereof Pending CN113045971A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113801551A (en) * 2021-08-26 2021-12-17 广东华润涂料有限公司 Two-component coating composition and articles made therefrom
CN114989708A (en) * 2022-03-02 2022-09-02 深圳市精彩科技有限公司 Odor-free polyurea coating and preparation method thereof
CN114989706A (en) * 2022-03-02 2022-09-02 深圳市精彩科技有限公司 Polyurea coating and preparation method thereof
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CN114989706B (en) * 2022-03-02 2024-02-09 深圳市精彩科技有限公司 Polyurea coating and preparation method thereof
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