CN111423798A - Water-based polyurea coating material and preparation method thereof - Google Patents
Water-based polyurea coating material and preparation method thereof Download PDFInfo
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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
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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
- C09D175/04—Polyurethanes
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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
- 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
- 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
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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
- 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
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention relates to application of nanotechnology in the field of coating materials, in particular to a water-based polyurea coating material and a preparation method thereof. The two-component polyurethane adhesive is composed of A, B two components, wherein A is a prepolymer taking modified isocyanate as a main body, and B is a curing agent taking silicate aqueous solution as a main body, and the two-component polyurethane adhesive is characterized in that: the water-based polyurea coating material A is added with a surfactant A, wherein the surfactant A is one or more of phosphate surfactants, and the addition amount of the surfactant A accounts for 0.001-10 parts by weight of the component A (the component A is calculated according to 100 parts by weight). The specific surfactant is added into the water-based polyurea coating material, so that the compatibility of each component in a system is improved, the particle size of particles generated by the system is reduced, the molecular weight of an in-situ polymer is increased, and the density of the system is increased, so that the corrosion resistance of the coating (such as salt spray resistance, acid, alkali, solvent and other medium soaking capacities) is improved.
Description
Technical Field
The invention relates to application of nanotechnology in the field of coating materials, in particular to a water-based polyurea coating material and a preparation method thereof.
Background
Nanotechnology is an emerging technology that has emerged in recent years and brings about a significant revolution in the field of materials science, and since the properties of surface materials involved in corrosion protection are determined by the microstructure, the emergence and application of nanotechnology will undoubtedly bring about a great opportunity for the development of corrosion control technology.
Researches show that the comprehensive performance of the organic coating anticorrosive material can be improved by modifying the organic coating anticorrosive material by utilizing the nanotechnology, particularly the mechanical strength, hardness and adhesive force of the material are increased, and the light resistance, aging resistance, weather resistance and the like are improved. E.g. TiO, SiO2Nano particles of ZnO, FeO, etc. have scattering action to ultraviolet ray and the nano particles are addedThe rice material can effectively enhance the ultraviolet resistance of the material and obviously improve the aging resistance. By introducing a small amount of nano particles into the material, the sealing property of the material can be improved, and better waterproof and anticorrosion effects can be achieved. For inorganic coating materials, the functions of obviously improving the plasticity and the toughness of the inorganic coating materials can be achieved if the structure of the inorganic coating materials is subjected to nanocrystallization. There are several patents currently available for modifying corrosion-resistant materials by nanotechnology. However, in general, the technology is only in the starting stage, and has great development prospect.
Generally, the method for introducing the inorganic nanoparticles adopts a melting and equal external mixing method, but gaps exist between inorganic particles and a system polymer, the inorganic particles cannot be completely infiltrated into an interface, the particles are easy to agglomerate and disperse unevenly, and for the anticorrosive coating, the system mostly depends on physical barrier to protect a base material, so that the system cannot be dense and directly cause the reduction of the anticorrosive performance. Compared with the method, the interface between the inorganic particles generated in situ by the system and the polymer of the system is more closely connected, the density of the system is higher, and the inorganic particles generated in situ by the system are undoubtedly smaller in size and uniform in distribution, so the method for generating the inorganic particles in situ is emphasized in recent years.
Patents HU212033 and US5622999 disclose methods for controlling the reaction rate in water-in-oil emulsions of water glass/polyisocyanate using certain small molecular weight phosphoric acid esters, in particular small molecular aliphatic phosphoric acid esters and small molecular aromatic phosphoric acid esters as catalysts and plasticizers. And the initials of the three main materials are taken, and the material is named as 3P resin. And the reaction time can be controlled between a few seconds to several hours. However, the size of the resulting polysilicic acid/polysilicate particles is in the range of 5-50 μm, with larger particles and a wider range. In addition, the product as a coating material has another disadvantage that the inorganic particles are too large in size and easily have gaps, so that the compactness of the system is not enough. The corrosion resistance is reduced.
Patent CN1993398A provides a hybrid resin with improved mechanical and fracture mechanical properties on the above mentioned patent substrates, including containing vinyl esters and/or polyesters. The above mixed resin reduces the silicate size to 1-5 μm, and the mechanical properties of the product are improved accordingly. But also as an anticorrosive coating, the compactness of the system is not enough to bear the invasion of corrosive gas.
International patent WO13/016370 produces polysilicic acid/polyurethane nanocomposites by reacting polysilicic acid with polyisocyanates by adding certain polyols and reduces the particle size in W/O emulsions by different emulsifiers that change the interfacial tension by creating compatibility between the hydrophilic polysilicic acid and the hydrophobic organic component with hydrophilic polyols. However, due to the introduction of the polyol, the system generates partial polyurethane, but the salt fog resistance of the polyurethane is poor, and the corrosion resistance of the system is seriously reduced.
Therefore, the invention aims to adopt a specific surfactant to improve the compatibility of each component in a system, reduce the particle size of particles generated by the system, increase the molecular weight of an in-situ polymer and increase the compactness of the system, thereby improving the corrosion resistance of a coating (such as salt spray resistance, acid, alkali, solvent and other medium soaking capacities).
Disclosure of Invention
In order to solve the above problems, the present invention provides an aqueous polyurea coating material and a method for preparing the same.
In order to achieve the purpose, the invention adopts the technical scheme that:
a water-based polyurea coating material comprises A, B two components, wherein A is a prepolymer taking modified isocyanate as a main body, B is a curing agent taking silicate aqueous solution as a main body, a surfactant A is added into the component A of the water-based polyurea coating material, the surfactant A is one or more of phosphate surfactants, and the addition amount of the surfactant A accounts for 0.001-10 parts by weight of the component A (the component A is calculated according to 100 parts by weight).
The surfactant A also comprises other conventional surfactants, and the addition amount of the conventional surfactants is 0.001-8 parts by weight of the component A (the component A is calculated by 100 parts); other conventional types of surfactants include, but are not limited to, fatty alcohol polyoxyethylene ether-based surfactants.
The phosphate ester surfactant is an anionic or nonionic surfactant containing phosphate ester or phosphate ester salt.
The phosphate ester surfactant is prepared by reacting fatty ether, fatty alcohol or alkanol amide compound with phosphate ester and then neutralizing with alkali.
The emulsifying capacity of the component A and the component B in the use system is improved, and other surfactants have little effect in the system but need to be compounded for use by virtue of the application of the phosphate surfactant. The system is a heterogeneous reaction system, the component A is an oil phase, the component B is a water phase, and the reaction is polymerized by an interface contacted with A, B, so that the reaction degree of the component A, B can be increased by improving the emulsifying capacity, and the particle size of generated in-situ particles is reduced.
The phosphate surfactant is one or more of alkyl phosphate, alkyl phosphate ester salt, aryl phosphate ester salt, fatty alcohol-polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, alkylolamide phosphate salt, high-molecular polyphosphate, imidazoline phosphate or siloxane phosphate; high molecular polyphosphate esters and alkyl (aryl) phosphate esters are preferred.
The alkyl (aryl) phosphate comprises one or a mixture of but not limited to alkyl (aryl) phosphate monoester, alkyl (aryl) phosphate diester and alkyl (aryl) phosphate triester, and the structures of the three phosphate salts are shown in the following figures:
wherein R is a C8 to C18 alkyl group, which is the most important factor affecting the surfactant, and M is K+、Na+Or diethanolamine, triethanolamine, and the like.
The fatty alcohol (alkylphenol) polyoxyethylene ether phosphate includes, but is not limited to, one or a mixture of fatty alcohol polyoxyethylene phosphate, polyoxyethylene stearamide phosphate, polyoxyethylene fatty amine phosphate and the like. The structural formula is shown as the following figure:
the high molecular phosphate ester includes but is not limited to different n polyoxyethylene stearamide ether C17H35CONH(CH2CH2O)nH, and the like.
The aqueous nano particle modified polyurethane/polyurea coating material is formed by mixing a component A and a component B according to the proportion of 1:1-3: 1; wherein, the component A comprises 20 to 80 portions of modified isocyanate, 0.001 to 10 portions of surfactant A, 0.01 to 20 portions of catalyst A, 5 to 70 portions of plasticizer and 0 to 30 portions of pigment/filler (pigment or filler) according to 100 portions; the component B comprises 40-60 parts of silicate, 40-60 parts of water, 0.001-10 parts of surfactant B and 0.001-10 parts of catalyst B according to 100 parts of water;
wherein the surfactant A is 0.001-10 parts of phosphate surfactant and 0.001-10 parts of conventional surfactant.
The modified isocyanate is one or more of isocyanate, blocked isocyanate, isocyanate monomer, bifunctional isocyanate prepolymer and polyfunctional isocyanate prepolymer.
The catalyst is one or more of tertiary amine catalyst, fatty amine catalyst or alcohol amine catalyst;
the catalyst A is an oil-soluble polyurethane catalyst, and comprises one or more of pyridine catalysts (such as pyridine, N-N' -dimethylpyridine) and organic tin catalysts (such as dibutyltin dilaurate and stannous octoate).
The catalyst B is a water-soluble polyurethane catalyst, and includes but is not limited to tertiary amine catalysts or alcohol amine catalysts, such as one or more of triethylene diamine, cyclohexyl methyl tertiary amine, pentamethyl diamine alkyl triamine, N', N-dimethyl benzylamine, dimethyl ethanolamine and the like.
The surfactant B is a nonionic surfactant, including but not limited to polyoxyethylene ether surfactants of alkyl phenol;
the silicate is water glass and/or water solution of sodium silicate and potassium silicate, and has modulus of 2.0-6.0.
The pigment is conventional organic/inorganic pigment such as iron oxide red, iron oxide yellow, ultramarine blue, phthalocyanine green, etc., and the filler is conventional filler such as bentonite, silicon dioxide, etc.
① adding modified isocyanate into a dispersion kettle according to the proportion, then adding catalyst, plasticizer, phosphate surfactant and other conventional surfactants in sequence, stirring for 10-20min, adding 0-30 parts of pigment/filler (pigment or filler) into the uniformly stirred slurry, dispersing for 1-2 h by adopting 1000-2000r until the slurry is stable, filtering to obtain component A;
② adding silicate, surfactant and catalyst into deionized water at the above ratio, dissolving to obtain clear and transparent solution, and filtering to obtain component B;
③ mixing the above obtained component A and component B at a ratio of 1:1-3:1 (mixing at present) to obtain the coating material.
In the step ②, the silicate is added into deionized water according to the proportion, and the high-modulus silicate is dissolved at 50-70 ℃ and 3-4MPa until the silicate is clear and transparent.
Compared with the prior art, the invention has the following advantages:
the specific surfactant is added into the water-based polyurea coating material, so that the compatibility of each component in a system is improved, the particle size of particles generated by the system is reduced, the molecular weight of an in-situ polymer is increased, and the density of the system is increased, so that the corrosion resistance of the coating (such as salt spray resistance, acid, alkali, solvent and other medium soaking capacities) is improved; the method specifically comprises the following steps:
① the water-based polyurea coating material of the invention improves the strength of the coating material by using the in-situ generated inorganic nano particles, improves the two-phase reaction activity by adding the specific type of surfactant, reduces the particle size of the generated particles, further improves the density of the coating, increases the emulsifying capacity of the system, solves the problem of the dispersion of the body oil/water two phases, leads the reaction degree to be higher and leads the particle size of the inorganic particles generated in the in-situ system to be smaller.
② the material of the invention reduces the in-situ generated particle size of the system by adding the surfactant containing phosphate ester, reduces the size of the generated inorganic particles, increases the density of the system and improves the corrosion resistance of the coating.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
An inorganic nanoparticle modified polyurethane/polyurea material is prepared from the following components in percentage by weight:
note: fatty alcohol polyoxyethylene ether phosphate is AEO-9 phosphate
The antifoaming agent is Tego 900
The leveling agent is Tego410
Wetting agent is BYK 2151
The catalyst is Niax A-1
Meanwhile, the defoaming agent, the leveling agent and the wetting agent in the formula can be correspondingly replaced according to the conventional auxiliary agents for preparing the coating material.
The preparation method of the inorganic nanoparticle modified polyurethane/polyurea material comprises the following steps:
① adding 50 parts of modified polymeric MDI into a dispersion kettle, sequentially adding 6 parts of triethyl phosphate and 29 parts of triphenyl phosphate, and stirring for 10 min;
② adding 3 parts of carbon black and 10 parts of bentonite into the slurry, and dispersing for 1-2 hours by adopting 1000-2000r until the slurry is stable;
③ adding wetting agent 0.3 parts, leveling agent 0.4 parts, and defoaming agent 0.3 parts in sequence into the stable slurry, stirring for 10min, and filtering to obtain component A.
④ adding 39.9 parts of silicate and 0.1 part of catalyst into 60 parts of deionized water to be dissolved until the solution is clear and transparent, and filtering to obtain a component B.
⑤ the coating material is obtained by mixing the component A and the component B at a ratio of 1.3:1-2.3:1 (now mixed).
Examples 2 to 25
The fatty alcohol-polyoxyethylene ether phosphate in the formulation of example 1 was replaced as shown in table 1, and the other compositions and proportions were unchanged, and the inorganic nanoparticle-modified polyurethane/polyurea coating material with different components and proportions was obtained according to the preparation method described in example 1.
Wherein, the system material without any additional phosphate ester surfactant added in the system is used as a comparison 1.
Table 1 examples of the catalyst types
Note that: examples 1-25 of table 1 phosphate ester surfactants performance tests were performed on the coating materials obtained in the above examples and comparative examples from fine chemistry procurement (see tables 2 and 3):
the test is according to ISO-12944 anticorrosion protection of steel structures by paint protection systems.
TABLE 2 Corrosion resistance test data for various examples
From the corrosion resistance data in Table 2, it can be seen that the salt fog resistance of the products of examples 1-25 is over 1100h, while the salt fog resistance of the commercial aqueous products is about 500 h. As can be seen from the above examples 1-25, in the example 19, the salt spray resistance is 3200h, the paint film is intact, and the phenomena of foaming, rusting, falling off and the like do not exist, meanwhile, after 3000h, the corrosion spread is mm, and the adhesion force after corrosion is 7.5MPa, which shows that the corrosion resistance of the product is good. In addition, the salt spray resistance of the products in examples 1-13 is basically between 1000-2000h, and the salt spray resistance of the products in examples 14-25 can reach more than 2000h, which shows that the phosphate surfactants reduce the size of generated inorganic particles in the system, increase the density of the system, and improve the corrosion resistance of the coating, thereby improving the protection capability of the coating on the metal base material.
Claims (10)
1. A water-based polyurea coating material consists of A, B two components, wherein A is a prepolymer taking modified isocyanate as a main body, and B is a curing agent taking silicate aqueous solution as a main body, and the coating material is characterized in that: the water-based polyurea coating material A is added with a surfactant A, wherein the surfactant A is one or more of phosphate surfactants, and the addition amount of the surfactant A accounts for 0.001-10 parts by weight of the component A (the component A is calculated according to 100 parts by weight).
2. The aqueous polyurea coating material of claim 1, wherein: the surfactant A also comprises other conventional surfactants, and the addition amount of the conventional surfactants is 0.001-8 parts by weight of the component A (the component A is calculated by 100 parts).
3. The aqueous polyurea coating material of claim 1, wherein: the phosphate ester surfactant is an anionic or nonionic surfactant containing phosphate ester or phosphate ester salt.
4. The aqueous polyurea coating material according to claim 1 or 3, wherein: the phosphate ester surfactant is prepared by reacting fatty ether, fatty alcohol or alkanol amide compound with phosphate ester and then neutralizing with alkali.
5. The aqueous polyurea coating material of claim 4, wherein: the phosphate ester surfactant is one or more of alkyl phosphate, alkyl phosphate ester salt, aryl phosphate ester salt, fatty alcohol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, alkyl alcohol amide phosphate salt, high-molecular polyphosphate ester salt, imidazoline phosphate ester salt or siloxane phosphate ester.
6. The aqueous polyurea coating material of claim 1, wherein: the water-based polyurea coating material is formed by mixing a component A and a component B according to the proportion of 1:1-3: 1; wherein, the component A comprises 20 to 80 portions of modified isocyanate, 0.001 to 10 portions of surfactant A, 0.01 to 20 portions of catalyst A, 5 to 70 portions of plasticizer and 0 to 30 portions of pigment/filler according to 100 portions; the component B comprises 40-60 parts of silicate, 40-60 parts of water, 0.001-10 parts of surfactant B and 0.001-10 parts of catalyst B according to 100 parts of water;
wherein the surfactant A is 0.001-10 parts of phosphate surfactant and 0.001-8 parts of conventional surfactant.
7. The aqueous polyurea coating material of claim 6, wherein: the modified isocyanate is one or more of isocyanate, blocked isocyanate, isocyanate monomer, bifunctional isocyanate prepolymer and polyfunctional isocyanate prepolymer.
8. The aqueous polyurea coating material as claimed in claim 6, wherein: the catalyst A is an oil-soluble polyurethane catalyst; the catalyst B is a water-soluble polyurethane catalyst.
9. A method for preparing the aqueous polyurea coating material according to claim 1, wherein:
① adding the modified isocyanate into the dispersing kettle according to the above proportion, then adding the catalyst, the plasticizer, the phosphate ester surfactant and other conventional surfactants in turn, and stirring for 10-20 min;
adding 0-30 parts of pigment/filler into the uniformly stirred slurry, and dispersing for 1-2 hours by adopting 1000-2000r until the slurry is stable; filtering to obtain a component A;
② adding silicate, surfactant and catalyst into deionized water at the above ratio, dissolving to obtain clear and transparent solution, and filtering to obtain component B;
③ mixing the component A and the component B according to the ratio of 1:1-3:1 to obtain the coating material.
10. The method of claim 9, wherein the silicate is added to the deionized water at the above ratio in step ②, and the high modulus silicate is dissolved at 50-70 deg.C and 3-4MPa until it is clear and transparent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116904048A (en) * | 2023-07-06 | 2023-10-20 | 广东自然涂化工有限公司 | Anti-pulverization exterior wall silicate anticorrosive paint and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5622999A (en) * | 1991-06-03 | 1997-04-22 | Polinvent Fejleszto, Kivitelezo Es Ertekesito Kft | Polysilicic acid/polyisocyanate basic materials, binding materials and foams and process for preparing same |
| CN108570279A (en) * | 2018-05-02 | 2018-09-25 | 沈阳化工研究院有限公司 | A kind of nano modification coating material and preparation method thereof |
-
2019
- 2019-01-10 CN CN201910022642.4A patent/CN111423798A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5622999A (en) * | 1991-06-03 | 1997-04-22 | Polinvent Fejleszto, Kivitelezo Es Ertekesito Kft | Polysilicic acid/polyisocyanate basic materials, binding materials and foams and process for preparing same |
| CN108570279A (en) * | 2018-05-02 | 2018-09-25 | 沈阳化工研究院有限公司 | A kind of nano modification coating material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116904048A (en) * | 2023-07-06 | 2023-10-20 | 广东自然涂化工有限公司 | Anti-pulverization exterior wall silicate anticorrosive paint and preparation method and application thereof |
| CN116904048B (en) * | 2023-07-06 | 2024-09-27 | 北新嘉宝莉涂料集团股份有限公司 | Anti-pulverization exterior wall silicate anticorrosive paint and preparation method and application thereof |
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Application publication date: 20200717 |