Non-isocyanate polyurea and preparation method thereof, water-based non-isocyanate polyurea and preparation method thereof, and anticorrosive coating, waterproof coating and fire retardant coating containing the same

Abstract

The present invention provides a non-isocyanate polyurea and a preparation method thereof, an aqueous non-isocyanate polyurea and a preparation method thereof, and an anticorrosive coating, a waterproof coating and a fire retardant coating containing the same. The non-isocyanate polyurea has a structure represented by the following general formula (1), wherein R1 is a divalent residue obtained after removing two amino groups from a polyetheramine, and the polyetheramine is an amino-terminated polyoxypropylene diamine with a number average molecular weight in the range of 230 to 5000; R2 is a C2-C8 divalent aliphatic group or a divalent alicyclic group; and n is an integer of 30-300. The method according to the present invention can prepare non-isocyanate polyurea with a high reaction rate, and the product obtained by using the non-isocyanate polyurea obtained by the preparation method as a raw material has excellent application performance (anticorrosive performance, waterproof performance, fire resistance, etc.). #imgabs0#

Description

Technical Field

[0001] The present invention relates to the field of non-isocyanate polyurea products, and in particular, to a non-isocyanate polyurea and a preparation method thereof, a water-based non-isocyanate polyurea and a preparation method thereof, a one-component anticorrosive coating comprising the non-isocyanate polyurea, a one-component waterproof coating comprising the non-isocyanate polyurea, and a water-based non-isocyanate polyurea-based intumescent fire retardant coating comprising the non-isocyanate polyurea. Background Art

[0002] As one of the most advanced resins, polyurea can completely or partially replace traditional polyurethane, epoxy resin and polyolefin compounds, and has broad application prospects. Polyurea is mainly obtained by the reaction of isocyanate prepolymer and amine substances, and isocyanate is highly irritating and toxic, and the raw material for preparing isocyanate is also a highly toxic substance phosgene, which is extremely harmful to the human body and the environment. With the promotion of "green chemistry", the use of non-toxic and environmentally friendly raw materials to prepare non-isocyanate polyurea (NIPUR) has become a research hotspot at this stage, and the gradual replacement of traditional polyurea by NIPUR is an inevitable trend in the future development of the polyurea industry.

[0003] At present, there are few reports on the synthesis of non-isocyanate polyurea (NIPUR) in China. The existing synthesis methods often result in incomplete reactions and are accompanied by many side reaction products, which seriously affect the product quality and greatly limit the application and development of NIPUR.

[0004] In addition, as the public's requirements for environmental protection become more urgent and strict, in the field of new chemical materials, the preparation process of polymer resins is gradually shifting from solvent-based to water-based. As a new type of water-based polymer, water-based polyurea has been a hot topic in the research of polyurea coatings in recent years. Water-based polyurea has the advantages of simple construction operation, low cost, and more practical products. It uses water as a dispersion medium and meets the requirements of environmental protection regulations. However, it still faces some problems such as poor comprehensive performance of the coating, poor water resistance of the coating, and low gloss, which to a certain extent restricts the development of water-based polyurea.

[0005] Therefore, the field of water-based polyurea urgently needs to develop a product with high physical properties, excellent coating water resistance and long service life so as to be applied in a wider range of fields, thereby promoting the application and development of water-based polyurea.

[0006] As the main component of coatings, film-forming substances are mainly used to firmly adhere the coatings to the surface of materials and form a continuous coating film. Therefore, the performance of film-forming substances determines the performance of coatings. At present, coating products with traditional resins (such as polyurethane, epoxy resin or acrylic resin) as film-forming substances are limited by the physical and chemical properties of the resins themselves, which greatly restricts the application and development of anti-corrosion coatings, waterproof coatings and fire-retardant coatings.

[0007] Therefore, the coatings industry is in urgent need of developing coatings products with high physical and chemical properties and long service life to promote the application and development of coatings products. Summary of the invention

[0008] Based on the above-stated problems, the purpose of the present invention is to provide a non-isocyanate polyurea and a preparation method thereof, a water-based non-isocyanate polyurea and a preparation method thereof, and an anti-corrosion coating, a waterproof coating and a fire retardant coating comprising the same, so as to solve the deficiencies in the prior art. To solve the above problems, the present invention first provides a non-isocyanate polyurea, which has a high reaction rate and a simple process. In addition, the product prepared using the synthesized non-isocyanate polyurea as a key raw material has excellent application performance.

[0009] Specifically, the non-isocyanate polyurea according to the present invention has good physical and chemical properties. In addition, when the non-isocyanate polyurea according to the present invention is used as a key raw material to prepare a waterproof coating, the resulting coating film has excellent physical properties such as elongation at break and tensile strength; and when the polyurea synthesized using the non-isocyanate polyurea according to the present invention as a key raw material is used as a film-forming substance to prepare an anti-corrosion coating, the resulting coating film has excellent corrosion resistance, high physical properties and a long service life; and when the water-based polyurea synthesized using the non-isocyanate polyurea according to the present invention as a key raw material is used as a film-forming substance to prepare an intumescent fire-retardant coating, the resulting coating film has excellent fire resistance, good water resistance and excellent bonding strength.

[0010] The inventors have completed the present invention after intensive and careful research.

[0011] According to one aspect of the present invention, there is provided a non-isocyanate polyurea having a structure represented by the following general formula (1):

[0012]

[0013] General formula (1)

[0014] Wherein, R1 is a divalent residue obtained by removing two amino groups from a polyetheramine, wherein the polyetheramine is an amino-terminated polyoxypropylene diamine having a number average molecular weight in the range of 230 to 5000; R2 is a C2-C8 divalent aliphatic group or a divalent alicyclic group; and n is an integer of 30-300.

[0015] According to certain preferred embodiments of the present invention, the polyetheramine is an amino-terminated polyoxypropylenediamine having a number average molecular weight in the range of 400 to 2000.

[0016] According to certain preferred embodiments of the present invention, R2 is a C2-C6 divalent straight chain aliphatic group.

[0017] According to certain preferred embodiments of the present invention, n is an integer of 80-200.

[0018] According to another aspect of the present invention, there is provided a method for preparing the non-isocyanate polyurea as described above, the method comprising the following steps:

[0019] (1) mixing ethylene carbonate and polyetheramine and heating them to react, thereby obtaining a polyetheramine having hydroxyethyl formate end-capped at both ends;

[0020] (2) adding a C2-C8 aliphatic diamine and a catalyst to the polyetheramine end-capped with hydroxyethyl formate at both ends, mixing them evenly and heating them, reacting them under high pressure, and removing ethylene glycol by reduced pressure distillation after the reaction is completed;

[0021] (3) Cooling the product obtained in step (2) and slowly adding a first organic solvent thereto to obtain the non-isocyanate polyurea.

[0022] According to certain preferred embodiments of the present invention, the C2-C8 aliphatic diamine is selected from one or more of ethylenediamine, 1,2-propylenediamine, N-ethylethylenediamine, 1,4-butylenediamine, 1,3-cyclohexanedimethylamine, 1,3-propylenediamine, 1,5-pentanediamine, hexamethylenediamine, 2-methyl-1,3-propylenediamine, 2-methylpentanediamine and cyclohexanediamine.

[0023] According to certain preferred embodiments of the present invention, the catalyst is an organic nitrogen heterocyclic compound.

[0024] According to certain preferred embodiments of the present invention, the catalyst is selected from one or more of pyridine compounds, pyran compounds, quinoline compounds and pyrimidine compounds.

[0025] According to certain preferred embodiments of the present invention, the catalyst is selected from 2,3-dihydroxypyridine, 4,6-dimethylpyrimidine, 4-hydroxymethylpyrimidine, 3-hydroxy-6-methylpyridine, 4-benzylpyridine, tetrahydropyran, 3,4-dihydro-2H-pyran, 4-hydroxy-6-methyl-2-pyrone, N-methyltetrahydro-2H-pyran-4-amine, 7-hydroxyisoquinoline, 4-hydroxy-2-methylindole, 1-methylisoquinoline, One or more of 1,2,3,4-tetrahydroquinoline, 6,7-dihydro-5H-quinolin-8-one, 1,2,3,4-tetrahydroquinoline, 3,4-dihydro-7-hydroxy-2(1H)-quinolinone, 4-hydroxy-N-methyl-2-quinoline, 3-phenyl-4-[3H]quinazolinone, 5-methylpyrimidine, 2,4-dimethoxypyrimidine, 2,4,6-trimethoxypyrimidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0026] According to certain preferred embodiments of the present invention, the first organic solvent is selected from one or more of xylene, cyclohexane, acetone, cyclohexanone and dichloromethane.

[0027] According to certain preferred embodiments of the present invention, in step (1), the molar ratio of the ethylene carbonate to the polyetheramine is 1.8:1 to 2:1.

[0028] According to certain preferred embodiments of the present invention, in step (1), the reaction temperature of the reaction is 90-120° C., and the reaction time is 9-15 h.

[0029] According to certain preferred embodiments of the present invention, in step (2), the molar ratio of the polyetheramine end-capped with hydroxyethyl formate at both ends to the aliphatic diamine is 1:1 to 1:1.2.

[0030] According to certain preferred embodiments of the present invention, in step (2), the weight ratio of the catalyst to the aliphatic diamine is 1×10 -6 : 1 to 1×10 -3 : 1.

[0031] According to certain preferred embodiments of the present invention, in step (2), the reaction temperature of the reaction is 120-200° C., the reaction pressure is 15-20 MPa, and the reaction time is 12-24 h.

[0032] According to another aspect of the present invention, there is provided a method for preparing a water-based non-isocyanate polyurea, the method comprising the following steps:

[0033] (1) slowly adding a second organic solvent to the non-isocyanate polyurea described above and stirring uniformly;

[0034] (2) adding an emulsifier and water to the product prepared in step (1) under high-speed dispersion, and removing the second organic solvent by reduced pressure distillation after successful emulsification to obtain the water-based non-isocyanate polyurea.

[0035] According to certain preferred embodiments of the present invention, in step (1), the second organic solvent is ethyl acetate.

[0036] According to certain preferred embodiments of the present invention, the emulsifier in step (2) is selected from one or more of sodium lauryl sulfate, phenol ethylene oxide and phenol ethylene oxide.

[0037] According to certain preferred embodiments of the present invention, in step (2), based on 100% by weight of the non-isocyanate polyurea, the amount of the emulsifier added is 2-10% by weight.

[0038] According to certain preferred embodiments of the present invention, the ratio of the weight of the non-isocyanate polyurea to the weight of the added water in step (2) is in the range of 1:1 to 1:5.

[0039] According to another aspect of the present invention, a one-component non-isocyanate polyurea anti-corrosion coating is provided, which comprises: 50-80 parts by weight of the non-isocyanate polyurea described above, 10-30 parts by weight of rutile titanium dioxide, 0.5-1.5 parts by weight of a dispersant, 0.5-0.8 parts by weight of a defoamer, 0.1-0.3 parts by weight of a leveling agent, 0.3-0.6 parts by weight of an ultraviolet absorber and 2-20 parts by weight of a third organic solvent.

[0040] According to certain preferred embodiments of the present invention, in the one-component non-isocyanate polyurea anticorrosive coating:

[0041] The dispersant is an anionic wetting dispersant; and / or

[0042] The defoamer is a polyolefin solution defoamer; and / or

[0043] The leveling agent is selected from one or more of an organic silicon leveling agent and a modified acrylic leveling agent; and / or

[0044] The ultraviolet absorber is selected from one or more of benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, benzotriazole ultraviolet absorbers, substituted acrylonitrile ultraviolet absorbers and triazine ultraviolet absorbers; and / or

[0045] The third organic solvent is selected from one or more of butyl acetate, diethyl carbonate, propylene glycol methyl ether acetate and xylene.

[0046] According to another aspect of the present invention, a one-component non-isocyanate polyurea waterproof coating is provided, wherein the one-component non-isocyanate polyurea waterproof coating comprises: 25-50 parts by weight of the non-isocyanate polyurea described above, 15-30 parts by weight of a plasticizer, 20-30 parts by weight of a filler, 0.1-0.5 parts by weight of a defoamer and 3-10 parts by weight of a fourth organic solvent.

[0047] According to certain preferred embodiments of the present invention, in the one-component non-isocyanate polyurea waterproof coating:

[0048] The plasticizer is selected from one or more of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, trioctyl phosphate, citrate, and chlorinated paraffin plasticizers; and / or

[0049] The filler is selected from one or more of rutile titanium dioxide, kaolin, heavy calcium carbonate, barium sulfate, magnesium oxide, calcium oxide, wollastonite and talc; and / or

[0050] The defoamer is a polyolefin solution defoamer; and / or

[0051] The fourth organic solvent is selected from one or more of xylene, solvent oil, ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

[0052] According to another aspect of the present invention, there is provided a water-based non-isocyanate polyurea-based intumescent fire-retardant coating, which comprises: 25-40 parts by weight of a water-based non-isocyanate polyurea prepared according to the preparation method described above, 0.1-0.5 parts by weight of a defoamer, 0.5-1.2 parts by weight of a dispersant, 0.1-0.5 parts by weight of a pH regulator, 20-30 parts by weight of rutile titanium dioxide, 6-15 parts by weight of melamine, 6-15 parts by weight of pentaerythritol, 20-30 parts by weight of ammonium polyphosphate, 0.3-1 parts by weight of a thickener and 10-25 parts by weight of water.

[0053] According to certain preferred embodiments of the present invention, in the water-based non-isocyanate polyurea-based intumescent fire retardant coating:

[0054] The defoamer is selected from one or more of a mineral oil defoamer and a polyether-modified silicone defoamer; and / or

[0055] The dispersant is an anionic wetting dispersant; and / or

[0056] The pH regulator is an aqueous solution of reactive organosilicon; and / or

[0057] The thickener is a polyurethane modified polyether associative thickener.

[0058] Compared with the prior art in this field, the advantages of the present invention are:

[0059] 1) Non-isocyanate polyurea is prepared by a simple process using a specific organic heterocyclic compound catalyst;

[0060] 2) The non-isocyanate polyurea according to the present invention does not require polyisocyanate to participate in curing, and has better safety and environmental friendliness;

[0061] 3) According to the water-based non-isocyanate polyurea prepared from the non-isocyanate polyurea of ​​the present invention, the coating film has higher physical properties, such as tensile strength, elongation at break and tear strength;

[0062] 4) The one-component non-isocyanate polyurea anticorrosive coating according to the present invention has excellent anticorrosion performance, artificial aging resistance and substrate adhesion.

[0063] 5) The one-component non-isocyanate polyurea waterproof coating according to the present invention has higher physical properties, such as tensile strength, elongation at break and tear strength;

[0064] 6) The water-based non-isocyanate polyurea-based intumescent fire retardant coating according to the present invention has high fire resistance, water resistance and bonding strength. DETAILED DESCRIPTION

[0065] The present invention will be described in further detail below in conjunction with specific embodiments. It will be appreciated that other embodiments are contemplated and may be implemented without departing from the scope or spirit of the present invention. Therefore, the following detailed description is non-restrictive.

[0066] Unless otherwise indicated, all numbers used in the specification and claims to represent feature sizes, quantities and physicochemical properties should be understood as being modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the attached claims are approximate values, and those skilled in the art can use the teachings disclosed herein to seek to obtain the desired properties and appropriately change these approximate values. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0067] As mentioned above, there is an urgent need in the prior art to develop a non-isocyanate polyurea and a preparation method thereof, a water-based non-isocyanate polyurea and a preparation method thereof, and an anti-corrosion coating, a waterproof coating and a fire retardant coating containing the same.

[0068] The object of the present invention is to provide a non-isocyanate polyurea and a preparation method thereof, a water-based non-isocyanate polyurea and a preparation method thereof, and an anticorrosive coating, a waterproof coating and a fire retardant coating containing the same. The preparation process of the non-isocyanate polyurea according to the present invention is simple and low in cost. When the water-based non-isocyanate polyurea is used as a raw material to prepare the water-based non-isocyanate polyurea, the mechanical properties (including tensile strength, elongation at break, and tear strength) of the coating are excellent; and when the non-isocyanate polyurea is used as a film-forming substance to prepare an anticorrosive coating, the resulting coating has excellent corrosion resistance and high physical properties; and when the non-isocyanate polyurea is used as a film-forming substance to prepare a waterproof coating, the resulting coating has good elongation at break, tensile strength and tear strength; and when the water-based non-isocyanate polyurea prepared from the non-isocyanate polyurea is used as a film-forming substance to prepare an intumescent fire retardant coating, the resulting coating has excellent fire resistance, good water resistance and excellent bonding strength.

[0069] Specifically, according to a first aspect of the present invention, there is provided a non-isocyanate polyurea having a structure represented by the following general formula (1):

[0070]

[0071] General formula (1)

[0072] Wherein, R1 is a divalent residue obtained by removing two amino groups from a polyetheramine, wherein the polyetheramine is an amino-terminated polyoxypropylene diamine having a number average molecular weight in the range of 230 to 5000; R2 is a C2-C8 divalent aliphatic group or a divalent alicyclic group; and n is an integer of 30-300.

[0073] The polyetheramine is an amino-terminated polyoxypropylene diamine with a number average molecular weight in the range of 230 to 5000, preferably 400 to 3000, and more preferably 400-2000. The inventors of the present invention have found in their research that the use of linear amino-terminated polyoxypropylene diamine can significantly improve the physical properties (e.g., tensile strength, elongation at break, tear strength, etc.) and substrate adhesion of the non-isocyanate polyurea resin compared to the use of branched amino-terminated polyoxypropylene triamine. In addition, the specific selection of R1 derived from amino-terminated polyoxypropylene diamine in the non-isocyanate polyurea has an important influence on the performance of the anticorrosive coating and waterproof coating series products obtained by using the non-isocyanate polyurea as a film-forming substance. By controlling the number average molecular weight of the polyetheramine within the range of 230 to 5000, and optimizing the types and contents of other components in the anticorrosive coating and waterproof coating, the obtained coating product can perform well in terms of substrate adhesion, mechanical properties (e.g., tensile strength, elongation at break, tear strength, etc.) and anticorrosive properties (e.g., acid resistance, alkali resistance, salt water resistance, and salt spray resistance, etc.). In particular, when the number average molecular weight of the amino-terminated polyoxypropylene diamine is further controlled within the range of 400-2000, the comprehensive performance of the obtained anticorrosive coating involving substrate adhesion and anticorrosive properties is greatly improved, and even far exceeds the performance standard judged as "excellent" in the industry.

[0074] In addition, the inventors of the present invention have found that the specific type of R2 in the non-isocyanate polyurea according to the present invention has an important influence on the physical properties (e.g., tensile strength, elongation at break, tear strength, etc.) of the resulting non-isocyanate polyurea resin. According to the technical solution of the present invention, R2 is a C2-C8 divalent aliphatic group or a divalent alicyclic group.

[0075] Preferably, R2 can be a divalent residue obtained by removing two amino groups from one of the following divalent aliphatic groups or divalent alicyclic groups: ethylenediamine, 1,2-propylenediamine, N-ethylethylenediamine, 1,4-butylenediamine, 1,3-cyclohexanedimethylamine, 1,3-propylenediamine, 1,5-pentanediamine, hexanediamine, 2-methyl-1,3-propylenediamine, 2-methylpentanediamine and cyclohexanediamine.

[0076] In order to optimize the physical properties of the obtained non-isocyanate polyurea resin (including tensile strength, elongation at break and tear strength, etc.), R2 is a C2-C6 divalent straight chain aliphatic group, more preferably a C2-C4 divalent straight chain aliphatic group. Most preferably, R2 is a divalent residue obtained by removing two amino groups from one of ethylenediamine, 1,3-propylenediamine and 1,4-butylenediamine.

[0077] In the non-isocyanate polyurea according to the present invention, the number of polyurea repeating units n is in the range of 30-300. It should be particularly noted that the number of polyurea repeating units n also has an important influence on the physical properties (e.g., tensile strength, elongation at break, tear strength, etc.) of the obtained non-isocyanate polyurea resin. When the number of polyurea repeating units n is less than 30, the number of polyurea repeating units is small, and sufficient intermolecular forces cannot be formed, thereby affecting the tensile strength of the material. The material is too fragile and cannot withstand large deformation before breaking, and is not suitable as a film-forming material for conventional anticorrosive coatings, waterproof coatings, and fire-retardant coatings. On the other hand, when the number of polyurea repeating units n is greater than 300, the material becomes more rigid when cured, limiting its application as a film-forming material requiring flexibility. Preferably, in order to provide good physical properties (e.g., tensile strength, elongation at break, tear strength, etc.) while giving its product excellent other application properties (anticorrosive properties, waterproof properties, fire resistance, etc.), the number of polyurea repeating units n is in the range of 80-200.

[0078] According to a second aspect of the present invention, there is provided a method for preparing a non-isocyanate polyurea, the method comprising the following steps:

[0079] (1) mixing ethylene carbonate and polyetheramine and heating them to react to obtain a polyetheramine capped at both ends with hydroxyethyl formate;

[0080] (2) adding a C2-C8 aliphatic diamine and a catalyst to the polyetheramine end-capped with hydroxyethyl formate at both ends, mixing them evenly and heating them, reacting them under high pressure, and removing ethylene glycol by reduced pressure distillation after the reaction is completed;

[0081] (3) cooling the product obtained in step (2) and slowly adding a first organic solvent thereto to obtain the non-isocyanate polyurea,

[0082] The non-isocyanate polyurea has a structure represented by the following general formula (1):

[0083]

[0084] General formula (1)

[0085] Wherein, R1 is a divalent residue obtained by removing two amino groups from a polyetheramine, wherein the polyetheramine is an amino-terminated polyoxypropylene diamine having a number average molecular weight in the range of 230 to 5000; R2 is selected from a C2-C8 divalent aliphatic group or a divalent alicyclic group; and n is an integer of 30-300.

[0086] The polyetheramine is an amino-terminated polyoxypropylene diamine with a number average molecular weight in the range of 230 to 5000, preferably 400 to 3000, and more preferably 400-2000. The inventors of the present invention have found in their research that the use of linear amino-terminated polyoxypropylene diamine can significantly improve the physical properties (e.g., tensile strength, elongation at break, tear strength, etc.) and substrate adhesion of the non-isocyanate polyurea resin compared to the use of branched amino-terminated polyoxypropylene triamine. In addition, the specific selection of R1 derived from amino-terminated polyoxypropylene diamine in the non-isocyanate polyurea has an important influence on the performance of the anticorrosive coating and waterproof coating series products obtained by using the non-isocyanate polyurea as a film-forming substance. By controlling the number average molecular weight of the polyetheramine within the range of 230 to 5000 and optimizing the types and contents of other components in the anticorrosive coating and waterproof coating, the obtained coating product can perform well in terms of substrate adhesion, mechanical properties (e.g., tensile strength, elongation at break, tear strength, etc.) and anticorrosive properties (e.g., acid resistance, alkali resistance, salt water resistance, and salt spray resistance, etc.). In particular, when the number average molecular weight of the amino-terminated polyoxypropylene diamine is further controlled within the range of 400-2000, the comprehensive performance of the obtained anticorrosive coating involving substrate adhesion and anticorrosive properties is greatly improved, and even far exceeds the performance standard judged as "excellent" in the industry.

[0087] Specific examples of amino-terminated polyoxypropylene diamines that can be used in the present invention include: JEFFAMINE series products D230, D400, D2000, and D4000 produced and sold by Huntsman Company in the United States.

[0088] Preferably, the aliphatic diamine is selected from one or more of ethylenediamine, 1,2-propylenediamine, N-ethylethylenediamine, 1,4-butylenediamine, 1,3-cyclohexyldimethylamine, 1,3-propylenediamine, 1,5-pentanediamine, hexamethylenediamine, 2-methyl-1,3-propylenediamine, 2-methylpentanediamine and cyclohexanediamine.

[0089] According to certain preferred embodiments of the present invention, the catalyst is an organic nitrogen heterocyclic compound. Preferably, the catalyst is selected from one or more of pyridine compounds, pyran compounds, quinoline compounds and pyrimidine compounds. Specifically, the catalyst is selected from 2,3-dihydroxypyridine, 4,6-dimethylpyrimidine, 4-hydroxymethylpyrimidine, 3-hydroxy-6-methylpyridine, 4-benzylpyridine, tetrahydropyran, 3,4-dihydro-2H-pyran, 4-hydroxy-6-methyl-2-pyrone, N-methyltetrahydro-2H-pyran-4-amine, 7-hydroxyisoquinoline, 4-hydroxy-2-methylindole, 1-methylisoquinoline, 6,7- One or more of dihydro-5H-quinolin-8-one, 1,2,3,4-tetrahydroquinoline, 3,4-dihydro-7-hydroxy-2(1H)-quinolinone, 4-hydroxy-N-methyl-2-quinoline, 3-phenyl-4-[3H]quinazolinone, 5-methylpyrimidine, 2,4-dimethoxypyrimidine, 2,4,6-trimethoxypyrimidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0090] Optionally, an organic solvent is added to the reaction system to adjust the viscosity of the reaction system and the product non-isocyanate polyurea. Preferably, the first organic solvent is selected from one or more of xylene, cyclohexane, acetone, cyclohexanone and dichloromethane.

[0091] Preferably, the weight ratio of the polyetheramine to the added first organic solvent is in the range of 3:1 to 1:1.

[0092] Preferably, in step (1), the molar ratio of the ethylene carbonate to the polyetheramine is 1.8:1 to 2:1, more preferably 2:1.

[0093] Preferably, in step (1), the reaction temperature is 90-120° C. and the reaction time is 9-15 h.

[0094] Preferably, in step (2), the molar ratio of the polyetheramine end-capped with hydroxyethyl formate at both ends to the C2-C8 aliphatic diamine is 1:1 to 1:1.2.

[0095] Preferably, in step (2), the ratio of the weight of the catalyst to the sum of the weight of the hydroxyethyl formate-terminated polyetheramine and the aliphatic diamine is 1×10 -6 : 1 to 1×10 -3 : 1, preferably within the range of 5×10 -6 :1 to 5×10 -5 : 1, more preferably 8×10 -6 : 1 to 1×10 -5 : Within 1 range.

[0096] Preferably, in step (2), the reaction temperature is 120-200° C., the reaction pressure is 15-20 MPa, and the reaction time is 12-24 h.

[0097] The preparation method of the non-isocyanate polyurea according to the present invention can prepare the non-isocyanate polyurea under relatively mild reaction conditions and simple processes. Specifically, the organic nitrogen heterocyclic catalyst used in the present invention has the characteristics of high activity and high selectivity, and can efficiently catalyze the reaction between the polyetheramine capped at both ends by hydroxyethyl formate and the aliphatic diamine, achieve a high reaction rate and obtain a high-purity non-isocyanate polyurea. The non-isocyanate polyurea can be directly used for the subsequent preparation of water-based non-isocyanate polyurea, one-component polyurea anticorrosive coatings, one-component polyurea-based waterproof coatings, and water-based non-isocyanate polyurea-based intumescent fire retardant coatings, etc.

[0098] According to a third aspect of the present invention, there is provided a method for preparing a water-based non-isocyanate polyurea, the method comprising the following steps:

[0099] (1) slowly adding a second organic solvent to the non-isocyanate polyurea described above and stirring uniformly;

[0100] (2) adding an emulsifier and water to the product prepared in step (1) under high-speed dispersion; after successful emulsification, removing the second organic solvent by reduced pressure distillation at 55° C. to 60° C. and a pressure of −0.085 to 0.095 MPa, thereby obtaining the water-based non-isocyanate polyurea.

[0101] Preferably, in step (1), the second organic solvent is ethyl acetate.

[0102] According to certain preferred embodiments of the present invention, the emulsifier in step (2) is selected from one of sodium lauryl sulfate and alkylphenol polyoxyethylene ether or a mixture thereof, preferably sodium lauryl sulfate, for example, one of ST626 and ST627 provided by Beyotime can be used.

[0103] Preferably, in step (2), based on 100% by weight of the non-isocyanate polyurea, the amount of the emulsifier added is 3-7% by weight.

[0104] Preferably, the ratio of the weight of the non-isocyanate polyurea to the weight of the added water in step (2) is in the range of 1:1 to 1:5.

[0105] According to a fourth aspect of the present invention, a one-component non-isocyanate polyurea anti-corrosion coating is provided, wherein the one-component non-isocyanate polyurea anti-corrosion coating comprises: 50-80 parts by weight of the non-isocyanate polyurea described above, 10-30 parts by weight of rutile titanium dioxide, 0.5-1.5 parts by weight of a dispersant, 0.5-0.8 parts by weight of a defoaming agent, 0.1-0.3 parts by weight of a leveling agent, 0.3-0.6 parts by weight of an ultraviolet absorber and 2-20 parts by weight of a third organic solvent.

[0106] Preferably, the rutile titanium dioxide can be one or more of rutile titanium dioxide R902 and R105 provided by DuPont of the United States; the dispersant is an anionic wetting dispersant, for example, one or more of RHEOBYK 110 and RHEOBYK 111 provided by BYK of Germany can be used; the defoamer is a polyolefin solution defoamer, for example, one or more of BYK-1790 and BYK-1799 provided by BYK of Germany can be used; the leveling agent is one or more of an organic silicon leveling agent and a modified acrylic leveling agent, for example, one of RHEOBYK410 and RHEOBYK 411 provided by BYK of Germany can be used; the ultraviolet absorber is one or more of benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, benzotriazole ultraviolet absorbers, substituted acrylonitrile ultraviolet absorbers and triazine ultraviolet absorbers, for example, RIASORB UV-326 and RIASORB UV-326 produced by Tianjin Lianlong Company can be used. UV-928, RIASORB UV-360 or more; the third organic solvent is selected from one or more of butyl acetate, diethyl carbonate, propylene glycol methyl ether acetate and xylene.

[0107] According to a fifth aspect of the present invention, a one-component non-isocyanate polyurea waterproof coating is provided, wherein the one-component non-isocyanate polyurea waterproof coating comprises: 25-50 parts by weight of the non-isocyanate polyurea described above, 15-30 parts by weight of a plasticizer, 20-30 parts by weight of a filler, 0.1-0.5 parts by weight of a defoamer and 3-10 parts by weight of a fourth organic solvent.

[0108] Preferably, the plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, trioctyl phosphate, citrate, and chlorinated paraffin plasticizers; the filler is one or more of rutile titanium dioxide, kaolin, heavy calcium carbonate, barium sulfate, magnesium oxide, calcium oxide, wollastonite, and talc; the defoamer is a polyolefin solution defoamer, for example, one or more of BYK-1790 and BYK-1799 provided by BYK of Germany can be used; the fourth organic solvent is one or more of xylene, solvent oil, ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

[0109] According to a sixth aspect of the present invention, a water-based non-isocyanate polyurea-based intumescent fire-retardant coating is provided, wherein the water-based non-isocyanate polyurea-based intumescent fire-retardant coating comprises: 25-40 parts by weight of the water-based non-isocyanate polyurea described above, 0.1-0.5 parts by weight of a defoamer, 0.5-1.2 parts by weight of a dispersant, 0.1-0.5 parts by weight of a pH adjuster, 20-30 parts by weight of rutile titanium dioxide, 6-15 parts by weight of melamine, 6-15 parts by weight of pentaerythritol, 20-30 parts by weight of ammonium polyphosphate, 0.3-1 parts by weight of a thickener and 10-25 parts by weight of water.

[0110] Preferably, the defoamer is one or more of a mineral oil defoamer and a polyether-modified silicone defoamer, for example, one or more of BYK-8820 and BYK-8821 provided by BYK of Germany can be used; the dispersant is an anionic wetting dispersant, for example, one or more of RHEOBYK 110 and RHEOBYK 111 provided by BYK of Germany can be used; the pH adjuster is an aqueous solution of reactive silicone, for example, BS168 provided by Wacker of Germany can be used; the rutile titanium dioxide can be one or more of rutile titanium dioxide R902 and R105 provided by DuPont of the United States; the ammonium polyphosphate is type II ammonium polyphosphate with a degree of polymerization n≥1000 and a water solubility of ≤0.5g / 100ml, for example, Exolit AP 422 and Exolit AP 105 provided by Clariant of Germany can be used. 428; the thickener is a polyurethane modified polyether associative thickener, for example, one or more of RHEOBYK 420 and RHEOBYK425 provided by BYK of Germany can be used.

[0111] The present invention is described in more detail below in conjunction with the examples. It should be noted that these descriptions and examples are intended to facilitate the understanding of the present invention, rather than to limit the present invention. The protection scope of the present invention shall be subject to the attached claims.

[0112] Example

[0113] In the present invention, unless otherwise specified, the reagents used are commercial products and are used directly without further purification. In addition, the "%" mentioned is "% by weight", and the "parts" mentioned are "parts by weight".

[0114] Test Method

[0115] Tensile strength, elongation at break and tear strength test of non-isocyanate polyurea coating after curing

[0116] In the following examples and comparative examples, the tensile strength, elongation at break and tear strength of the non-isocyanate polyurea coating obtained in each example and comparative example after curing were measured. For specific measurement methods, refer to the relevant test methods in GB / T16777-2008 "Test Methods for Building Waterproof Coatings". Among them, if the tensile strength of the coating is greater than or equal to 20 MPa, it is determined that the tensile strength performance of the non-isocyanate polyurea is good and meets the basic requirements for the relevant properties of the non-isocyanate polyurea; if the tensile strength is greater than or equal to 30 MPa, it is determined that the tensile strength performance of the non-isocyanate polyurea is excellent. If the elongation at break is greater than or equal to 250%, it is determined that the ductility of the non-isocyanate polyurea is good and meets the basic requirements for the relevant properties of the non-isocyanate polyurea; if the elongation at break exceeds 450%, it is determined that the ductility of the non-isocyanate polyurea is excellent. If the tear strength is greater than or equal to 40 MPa, the non-isocyanate polyurea is judged to have good tear performance and meet the basic requirements for relevant performance of the non-isocyanate polyurea; if the tear strength is greater than or equal to 80 MPa, the non-isocyanate polyurea is judged to have excellent tear strength performance.

[0117] Tensile strength, elongation at break and tear strength testing of waterborne non-isocyanate polyurea after curing

[0118] In the following examples, the tensile strength, elongation at break and tear strength of the water-based non-isocyanate polyurea obtained in each example and comparative example after curing were measured. The specific measurement method is as follows:

[0119] The obtained water-based non-isocyanate polyurea emulsion is coated on a polytetrafluoroethylene plate with a size of 350 mm × 320 mm, so that the final coating thickness is 1.5 ± 0.2 mm. The polytetrafluoroethylene plate coated with the coating is dried for 2 days at 23 ° C and 50% humidity. It is then kept at a temperature of 23 ° C and a humidity of 50% for 4 days. Then, the tensile strength, elongation at break and tear strength of the obtained coating are tested according to the test method specified in GB-T16777-2008 "Test Methods for Building Waterproof Coatings". Among them, if the tensile strength is greater than or equal to 6.0 MPa, it is considered to meet the general industrial application requirements of water-based non-isocyanate polyurea emulsions; if the tensile strength is greater than or equal to 10 MPa, it is considered that the tensile strength performance of the water-based non-isocyanate polyurea emulsion is excellent. If the elongation at break is greater than or equal to 300%, it is considered to meet the general industrial application requirements of water-based non-isocyanate polyurea emulsions; if the elongation at break is greater than or equal to 460%, the elongation at break performance of the water-based non-isocyanate polyurea emulsion is considered to be excellent. If the tear strength is greater than or equal to 40N / mm, it is considered to meet the general industrial application requirements of water-based non-isocyanate polyurea emulsions; if the tear strength is greater than or equal to 80N / mm, the tear strength performance of the water-based non-isocyanate polyurea emulsion is considered to be excellent.

[0120] Salt spray resistance and acid and alkali resistance test of one-component non-isocyanate polyurea anticorrosive coating

[0121] The salt spray resistance and acid and alkali resistance of the one-component non-isocyanate polyurea anticorrosive coating obtained in each embodiment and comparative example are measured. For specific measurement methods, refer to the relevant test methods in JG / T 224-2007 "Anticorrosive Coatings for Steel Structures in Construction". Among them, if the acid resistance is greater than or equal to 96h, it is considered to meet the general industrial application requirements of anticorrosive coating materials for steel structures in construction; if the acid resistance is greater than or equal to 168h, it is considered that the anticorrosive coating for steel structures in construction has excellent acid resistance. If the alkali resistance is greater than or equal to 96h, it is considered to meet the general industrial application requirements of anticorrosive coating materials for steel structures in construction; if the alkali resistance is greater than or equal to 168h, it is considered that the anticorrosive coating for steel structures in construction has excellent alkali resistance. If the salt water resistance is greater than or equal to 120h, it is considered to meet the general industrial application requirements of anticorrosive coating materials for steel structures in construction; if the salt water resistance is greater than or equal to 240h, it is considered that the anticorrosive coating for steel structures in construction has excellent salt water resistance. If the salt spray resistance is greater than or equal to 500h, it is considered to meet the general industrial application requirements of anti-corrosion coating materials for steel structures for construction; if the salt spray resistance is greater than or equal to 1000h, it is considered that the anti-corrosion coating for steel structures for construction has excellent salt spray resistance.

[0122] Mechanical properties test of one-component non-isocyanate polyurea waterproof coating

[0123] The tensile strength and elongation at break of the one-component non-isocyanate polyurea waterproof coating obtained in each embodiment and comparative example were measured. For specific measurement methods, refer to the relevant test methods in GB / T 19250-2013 "Polyurethane Waterproof Coating". Among them, if the tensile strength is greater than or equal to 6 MPa, it is considered to meet the general industrial application requirements of polyurethane waterproof coating materials for construction; if the tensile strength of the coating film is greater than or equal to 12 MPa, the tensile strength performance of the polyurethane waterproof coating material for construction is considered to be excellent. If the elongation at break is greater than or equal to 250%, it is considered to meet the general industrial application requirements of polyurethane waterproof coating materials for construction; if the elongation at break is greater than or equal to 450%, if the tear strength is greater than or equal to 30N / mm, it is considered to meet the general industrial application requirements of polyurethane waterproof coating materials for construction; if the tear strength is greater than or equal to 40N / mm, the elongation at break performance of the polyurethane waterproof coating material for construction is considered to be excellent.

[0124] Physical property test and fire performance test of water-based non-isocyanate polyurea-based intumescent fire retardant coating

[0125] The physical properties and fire retardant properties of the water-based non-isocyanate polyurea-based intumescent fire retardant coatings obtained in each embodiment and comparative example were measured. For specific measurement methods, please refer to the relevant test methods in GB / T14907-2018 "Steel Structure Fire Retardant Coatings". Among them, if the bonding strength is greater than or equal to 0.15MPa, it is considered to meet the general industrial application requirements of intumescent steel structure fire retardant coating materials for construction; if the bonding strength is greater than or equal to 0.3MPa, it is considered that the intumescent steel structure fire retardant coating for construction has excellent bonding strength performance. If the water resistance is greater than or equal to 24h, it is considered to meet the general industrial application requirements of intumescent steel structure fire retardant coating materials for construction; if the water resistance is greater than or equal to 48h, it is considered that the intumescent steel structure fire retardant coating for construction has excellent water resistance. If the fire resistance is greater than or equal to 0.5h / 2mm, it is considered to meet the general industrial application requirements of the expanding steel structure fire retardant coating materials for construction; if the fire resistance is greater than or equal to 1.0h / 2mm, the expanding steel structure fire retardant coating for construction is considered to have excellent fire resistance.

[0126] Example 1

[0127] 100 g of polyetheramine Jeffamine D 2000 (functionality 2, number average molecular weight 2000) and 8.8 g of ethylene carbonate were placed in a 500 mL stainless steel reactor, stirred, and slowly heated to 110° C. and maintained for 12 hours to obtain a polyetheramine capped at both ends with hydroxyethyl formate.

[0128] 7.4 g of 1,3-propylenediamine and 0.001 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene were added to the polyetheramine end-capped with hydroxyethyl formate obtained in the above step, mixed evenly, heated to 170°C, and reacted for 15 hours under a pressure of 18 MPa. After the reaction was completed, the ethylene glycol produced by the reaction was removed by distillation under reduced pressure. After the system was cooled to about 80°C, xylene was slowly added to obtain non-isocyanate polyurea.

[0129] The structure of the non-isocyanate polyurea prepared above was characterized by conventional chemical analysis methods (gel permeation chromatography (GPC)). The results showed that the non-isocyanate polyurea had a structure represented by the above general formula (1), wherein n is 98.

[0130] Take 100 grams of the non-isocyanate polyurea obtained in the above steps, slowly add 20 grams of ethyl acetate, and stir until uniform. Under the condition of a disperser speed of 1000r / min, add 5 grams of emulsifier (ST626) and 200 grams of water in sequence, and emulsify at high speed for 2 hours. After successful emulsification, heat to 55°C under a pressure of -0.095MPa, and remove ethyl acetate by reduced pressure distillation to obtain the water-based non-isocyanate polyurea.

[0131] 80.0 parts by weight of the above-mentioned non-isocyanate polyurea, 12.0 parts by weight of rutile titanium dioxide R902, 1.0 parts by weight of dispersant RHEOBYK-110, and 0.5 parts by weight of defoamer BYK-1790 were mixed and dispersed at a high speed of 1000 r / min for 1 hour; then 0.2 parts by weight of leveling agent (RHEOBYK-410), 0.3 parts by weight of ultraviolet absorber RIASORB UV-360 and 6 parts by weight of butyl acetate were added, and dispersed at 500 r / min for 15 minutes to obtain a one-component non-isocyanate polyurea anticorrosive coating.

[0132] 50 parts by weight of the above-mentioned non-isocyanate polyurea, 20 parts by weight of dioctyl phthalate, 23 parts by weight of rutile titanium dioxide, and 0.3 parts by weight of defoamer BYK-1799 are mixed and dispersed at a high speed of 1000 r / min for 1 hour and then at a high speed of 1500 r / min for 1 hour; then 6.7 parts by weight of xylene are added and dispersed evenly to obtain a one-component non-isocyanate polyurea waterproof coating.

[0133] 30 parts by weight of the above-mentioned water-based non-isocyanate polyurea, 0.2 parts by weight of defoamer BYK-8820, 1 part by weight of dispersant RHEOBYK 110, 0.2 parts by weight of pH regulator BS 168, 20 parts by weight of rutile titanium dioxide R105, 9 parts by weight of melamine, 6 parts by weight of pentaerythritol, 22 parts by weight of ammonium polyphosphate Exolit AP 422, 0.6 parts by weight of thickener RHEOBYK420 and 11 parts by weight of water were dispersed at a speed of 800 r / min for 1 hour to obtain a water-based non-isocyanate polyurea-based intumescent fire retardant coating.

[0134] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0135] Example 2

[0136] 115 g of polyetheramine Jeffamine D 230 (functionality 2, number average molecular weight 230) and 88 g of ethylene carbonate were placed in a 500 mL stainless steel reactor, stirred, and slowly heated to 100° C. and maintained for 10 hours to obtain a polyetheramine capped at both ends with hydroxyethyl formate.

[0137] 60 g of ethylenediamine and 0.0025 g of 3,4-dihydro-7-hydroxy-2(1H)-quinolinone are added to the polyetheramine end-capped with hydroxyethyl formate obtained in the above step, mixed evenly, heated to 150° C., reacted at a pressure of 20 MPa for 21 hours, and after the reaction is completed, the ethylene glycol produced by the reaction is removed by distillation under reduced pressure. After the system is cooled to about 80° C., xylene is slowly added to obtain non-isocyanate polyurea.

[0138] The structure of the non-isocyanate polyurea prepared above was characterized by conventional chemical analysis methods (gel permeation chromatography (GPC)). The results showed that the non-isocyanate polyurea had a structure represented by the above general formula (1), wherein n is 186.

[0139] Take 100 grams of the non-isocyanate polyurea obtained in the above steps, slowly add 20 grams of ethyl acetate, and stir until uniform. Under the condition of a disperser speed of 1000r / min, add 3.5 grams of emulsifier (ST626) and 250 grams of water in sequence, and emulsify by high-speed dispersion for 2 hours. After successful emulsification, heat to 55°C under a pressure of -0.095MPa, and remove ethyl acetate by reduced pressure distillation to obtain the water-based non-isocyanate polyurea.

[0140] 55.0 parts by weight of the above-mentioned non-isocyanate polyurea, 28.0 parts by weight of rutile titanium dioxide R105, 1.3 parts by weight of dispersant RHEOBYK-110, and 0.5 parts by weight of defoamer BYK-1799 were mixed and dispersed at a high speed of 1000 r / min for 1 hour; then 0.2 parts by weight of leveling agent RHEOBYK 411, 0.5 parts by weight of ultraviolet absorber RIASORB UV-360 and 14.5 parts by weight of propylene glycol methyl ether acetate were added, and dispersed at 500 r / min for 15 minutes to obtain a one-component non-isocyanate polyurea anticorrosive coating.

[0141] 33 parts by weight of the above-mentioned non-isocyanate polyurea, 30 parts by weight of trioctyl phosphate, 29 parts by weight of heavy calcium carbonate, and 0.5 parts by weight of defoamer BYK-1799 are mixed and dispersed at a high speed of 1000 r / min for 1 hour and at a high speed of 1500 r / min for 1 hour; then 7.5 parts by weight of ethyl acetate are added and dispersed evenly to obtain a one-component non-isocyanate polyurea waterproof coating.

[0142] 36 parts by weight of the above-mentioned water-based non-isocyanate polyurea, 0.3 parts by weight of defoamer BYK-8820, 1 part by weight of dispersant RHEOBYK 110, 0.2 parts by weight of pH regulator BS 168, 14 parts by weight of rutile titanium dioxide R902, 9 parts by weight of melamine, 8 parts by weight of pentaerythritol, 23 parts by weight of ammonium polyphosphate Exolit AP 422, 0.5 parts by weight of thickener RHEOBYK425 and 8 parts by weight of water were dispersed at a speed of 800 r / min for 1 hour to obtain a water-based non-isocyanate polyurea-based intumescent fire retardant coating.

[0143] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0144] Example 3

[0145] 100 g of polyetheramine Jeffamine D 400 (functionality 2, number average molecular weight 400) and 44 g of ethylene carbonate were placed in a 500 mL stainless steel reactor, stirred, and slowly heated to 100° C. and maintained for 12 hours to obtain a polyetheramine capped at both ends with hydroxyethyl formate.

[0146] 58 g of hexamethylenediamine and 0.002 g of 7-hydroxyisoquinoline were added to the polyetheramine end-capped with hydroxyethyl formate obtained in the above step, mixed evenly, heated to 200°C, and reacted for 15 hours under a pressure of 16 MPa. After the reaction was completed, the ethylene glycol produced by the reaction was removed by distillation under reduced pressure. After the system was cooled to about 80°C, cyclohexane was slowly added to obtain non-isocyanate polyurea.

[0147] The structure of the non-isocyanate polyurea prepared above was characterized by conventional chemical analysis methods (gel permeation chromatography (GPC)). The results showed that the non-isocyanate polyurea had a structure represented by the above general formula (1), wherein n is 159.

[0148] Take 100 grams of the non-isocyanate polyurea obtained in the above steps, slowly add 20 grams of ethyl acetate, and stir until uniform. Under the condition of a disperser speed of 1000r / min, add 6 grams of emulsifier (ST626) and 200 grams of water in sequence, and emulsify at high speed for 2 hours. After emulsification is successful, heat to 55°C under a pressure of -0.095MPa, and remove ethyl acetate by reduced pressure distillation to obtain the water-based non-isocyanate polyurea.

[0149] 73.0 parts by weight of the above-mentioned non-isocyanate polyurea, 16.0 parts by weight of rutile titanium dioxide R105, 1.0 parts by weight of dispersant RHEOBYK 111, and 0.8 parts by weight of defoamer BYK-1790 were mixed and dispersed at a high speed of 1000 r / min for 1 hour; then 0.2 parts by weight of leveling agent (RHEOBYK-410), 0.4 parts by weight of ultraviolet absorber RIASORB UV-928 and 8.6 parts by weight of diethyl carbonate were added and dispersed at 500 r / min for 15 minutes to obtain a one-component non-isocyanate polyurea anticorrosive coating.

[0150] 44 parts by weight of the above-mentioned non-isocyanate polyurea, 23 parts by weight of dioctyl phthalate, 25 parts by weight of talc, and 0.5 parts by weight of defoamer BYK-1799 are mixed and dispersed at a high speed of 1000 r / min for 1 hour and at a high speed of 1500 r / min for 1 hour; then 7.5 parts by weight of propylene glycol methyl ether acetate are added and dispersed evenly to obtain a one-component non-isocyanate polyurea waterproof coating.

[0151] 25 parts by weight of the above-mentioned water-based non-isocyanate polyurea, 0.5 parts by weight of defoamer BYK-8821, 0.8 parts by weight of dispersant RHEOBYK 111, 0.2 parts by weight of pH regulator BS 168, 23 parts by weight of rutile titanium dioxide R105, 8 parts by weight of melamine, 11 parts by weight of pentaerythritol, 26 parts by weight of ammonium polyphosphate Exolit AP 422, 0.3 parts by weight of thickener RHEOBYK 420 and 5.2 parts by weight of water were dispersed at a speed of 800 r / min for 1 hour to obtain a water-based non-isocyanate polyurea-based intumescent fire retardant coating.

[0152] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0153] Example 4

[0154] 200 g of polyetheramine Jeffamine D 4000 (functionality: 2, number average molecular weight: 4000) and 8.8 g of ethylene carbonate were placed in a 500 mL stainless steel reactor, stirred, and slowly heated to 120° C. and maintained for 15 hours to obtain a polyetheramine capped at both ends with hydroxyethyl formate.

[0155] 8.8 g of 1,4-butanediamine and 0.002 g of 4-hydroxy-2-methylindole were added to the polyetheramine end-capped with hydroxyethyl formate obtained in the above step, mixed evenly, heated to 180°C, and reacted for 19 hours under a pressure of 17 MPa. After the reaction was completed, the ethylene glycol produced by the reaction was removed by distillation under reduced pressure. After the system was cooled to about 80°C, acetone was slowly added to obtain non-isocyanate polyurea.

[0156] The structure of the non-isocyanate polyurea prepared above was characterized by conventional chemical analysis methods (gel permeation chromatography (GPC)). The results showed that the non-isocyanate polyurea had a structure represented by the above general formula (1), wherein n is 82.

[0157] Take 100 grams of the non-isocyanate polyurea obtained in the above steps, slowly add 20 grams of ethyl acetate, and stir thoroughly until uniform. Under the condition of a disperser speed of 1000r / min, add 7 grams of emulsifier ST627 and 250 grams of water in sequence, and disperse at high speed for 2 hours for emulsification. After successful emulsification, heat to 55°C under a pressure of -0.095MPa, and remove ethyl acetate by reduced pressure distillation to obtain the water-based non-isocyanate polyurea.

[0158] 68.0 parts by weight of the above-mentioned non-isocyanate polyurea, 20.0 parts by weight of rutile titanium dioxide R902, 1.2 parts by weight of dispersant RHEOBYK-110, and 0.6 parts by weight of defoamer BYK-1790 were mixed and dispersed at a high speed of 1000 r / min for 1 hour; then 0.3 parts by weight of leveling agent (RHEOBYK-410), 0.4 parts by weight of ultraviolet absorber RIASORB UV-360 and 9.5 parts by weight of xylene were added, and dispersed at 500 r / min for 15 minutes to obtain a one-component non-isocyanate polyurea anticorrosive coating.

[0159] 44 parts by weight of the above-mentioned non-isocyanate polyurea, 23 parts by weight of dioctyl phthalate, 26 parts by weight of barium sulfate, and 0.5 parts by weight of defoamer BYK-1799 are mixed and dispersed at a high speed of 1000 r / min for 1 hour and then at a high speed of 1500 r / min for 1 hour; then 6.5 parts by weight of xylene are added and dispersed evenly to obtain a one-component non-isocyanate polyurea waterproof coating.

[0160] 26 parts by weight of the above-mentioned water-based non-isocyanate polyurea, 0.5 parts by weight of defoamer BYK-8821, 0.5 parts by weight of dispersant RHEOBYK 110, 0.5 parts by weight of pH regulator BS 168, 23 parts by weight of rutile titanium dioxide R105, 13 parts by weight of melamine, 12 parts by weight of pentaerythritol, 20 parts by weight of ammonium polyphosphate Exolit AP 422, 0.5 parts by weight of thickener RHEOBYK 425 and 4 parts by weight of water were dispersed at a speed of 800 r / min for 1 hour to obtain a water-based non-isocyanate polyurea-based intumescent fire retardant coating.

[0161] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0162] Example 5

[0163] 100 g of polyetheramine Jeffamine D 2000 (functionality 2, number average molecular weight 2000) and 8.8 g of ethylene carbonate were placed in a 500 mL stainless steel reactor, stirred, and slowly heated to 90° C. and maintained for 15 hours to obtain a polyetheramine capped at both ends with hydroxyethyl formate.

[0164] 11.6 g of 2-methylpentanediamine and 0.0015 g of 2,4-dimethoxypyrimidine were added to the polyetheramine end-capped with hydroxyethyl formate obtained in the above step, mixed evenly, heated to 160°C, and reacted for 18 hours under a pressure of 18 MPa. After the reaction was completed, the ethylene glycol produced by the reaction was removed by distillation under reduced pressure. After the system was cooled to about 80°C, xylene was slowly added to obtain non-isocyanate polyurea.

[0165] The structure of the non-isocyanate polyurea prepared above was characterized by conventional chemical analysis methods (gel permeation chromatography (GPC)). The results showed that the non-isocyanate polyurea had a structure represented by the above general formula (1), wherein n is 103.

[0166] Take 100 grams of the non-isocyanate polyurea obtained in the above steps, slowly add 20 grams of ethyl acetate, and stir until uniform. Under the condition of a disperser speed of 1000r / min, add 5 grams of emulsifier (ST626) and 200 grams of water in sequence, and emulsify at high speed for 2 hours. After successful emulsification, heat to 55°C under a pressure of -0.095MPa, and remove ethyl acetate by reduced pressure distillation to obtain the water-based non-isocyanate polyurea.

[0167] 73.0 parts by weight of the above-mentioned non-isocyanate polyurea, 16.0 parts by weight of rutile titanium dioxide R105, 1.0 parts by weight of dispersant RHEOBYK 111, and 0.8 parts by weight of defoamer BYK-1790 were mixed and dispersed at a high speed of 1000 r / min for 1 hour; then 0.2 parts by weight of leveling agent (RHEOBYK-410), 0.4 parts by weight of ultraviolet absorber RIASORB UV-928 and 8.6 parts by weight of diethyl carbonate were added and dispersed at 500 r / min for 15 minutes to obtain a one-component non-isocyanate polyurea anticorrosive coating.

[0168] 50 parts by weight of the above-mentioned non-isocyanate polyurea, 20 parts by weight of dioctyl phthalate, 23 parts by weight of rutile titanium dioxide, and 0.3 parts by weight of defoamer BYK-1799 are mixed and dispersed at a high speed of 1000 r / min for 1 hour and then at a high speed of 1500 r / min for 1 hour; then 6.7 parts by weight of xylene are added and dispersed evenly to obtain a one-component non-isocyanate polyurea waterproof coating.

[0169] 30 parts by weight of the above-mentioned water-based non-isocyanate polyurea, 0.2 parts by weight of defoamer BYK-8820, 1 part by weight of dispersant RHEOBYK 110, 0.2 parts by weight of pH regulator BS 168, 20 parts by weight of rutile titanium dioxide R105, 9 parts by weight of melamine, 6 parts by weight of pentaerythritol, 22 parts by weight of ammonium polyphosphate Exolit AP 422, 0.6 parts by weight of thickener RHEOBYK420 and 11 parts by weight of water were dispersed at a speed of 800 r / min for 1 hour to obtain a water-based non-isocyanate polyurea-based intumescent fire retardant coating.

[0170] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0171] Example 6

[0172] 100 g of polyetheramine Jeffamine D 400 (functionality 2, number average molecular weight 400) and 44 g of ethylene carbonate were placed in a 500 mL stainless steel reactor, stirred, and slowly heated to 100° C. and maintained for 12 hours to obtain a polyetheramine capped at both ends with hydroxyethyl formate.

[0173] 51 g of 1,5-pentanediamine and 0.002 g of 4,6-dimethylpyrimidine were added to the polyetheramine end-capped with hydroxyethyl formate obtained in the above step, mixed evenly, heated to 200°C, and reacted for 11 hours under a pressure of 20 MPa. After the reaction was completed, the ethylene glycol produced by the reaction was removed by distillation under reduced pressure. After the system was cooled to about 80°C, cyclohexane was slowly added to obtain non-isocyanate polyurea.

[0174] The structure of the non-isocyanate polyurea prepared above was characterized by conventional chemical analysis methods (gel permeation chromatography (GPC)). The results showed that the non-isocyanate polyurea had a structure represented by the above general formula (1), wherein n is 146.

[0175] Take 100 grams of the non-isocyanate polyurea obtained in the above steps, slowly add 20 grams of ethyl acetate, and stir until uniform. Under the condition of a disperser speed of 1000r / min, add 6 grams of emulsifier (ST626) and 200 grams of water in sequence, and emulsify at high speed for 2 hours. After emulsification is successful, heat to 55°C under a pressure of -0.095MPa, and remove ethyl acetate by reduced pressure distillation to obtain the water-based non-isocyanate polyurea.

[0176] 73.0 parts by weight of the above-mentioned non-isocyanate polyurea, 16.0 parts by weight of rutile titanium dioxide R105, 1.0 parts by weight of dispersant RHEOBYK 111, and 0.8 parts by weight of defoamer BYK-1790 were mixed and dispersed at a high speed of 1000 r / min for 1 hour; then 0.2 parts by weight of leveling agent (RHEOBYK-410), 0.4 parts by weight of ultraviolet absorber RIASORB UV-928 and 8.6 parts by weight of diethyl carbonate were added and dispersed at 500 r / min for 15 minutes to obtain a one-component non-isocyanate polyurea anticorrosive coating.

[0177] 44 parts by weight of the above-mentioned non-isocyanate polyurea, 23 parts by weight of dioctyl phthalate, 26 parts by weight of barium sulfate, and 0.5 parts by weight of defoamer BYK-1799 are mixed and dispersed at a high speed of 1000 r / min for 1 hour and then at a high speed of 1500 r / min for 1 hour; then 6.5 parts by weight of xylene are added and dispersed evenly to obtain a one-component non-isocyanate polyurea waterproof coating.

[0178] 26 parts by weight of the above-mentioned water-based non-isocyanate polyurea, 0.5 parts by weight of defoamer BYK-8821, 0.5 parts by weight of dispersant RHEOBYK 110, 0.5 parts by weight of pH regulator BS 168, 23 parts by weight of rutile titanium dioxide R105, 13 parts by weight of melamine, 12 parts by weight of pentaerythritol, 20 parts by weight of ammonium polyphosphate Exolit AP 422, 0.5 parts by weight of thickener RHEOBYK 425 and 4 parts by weight of water were dispersed at a speed of 800 r / min for 1 hour to obtain a water-based non-isocyanate polyurea-based intumescent fire retardant coating.

[0179] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0180] Comparative Example 1

[0181] A non-isocyanate polyurea and a derivative of the non-isocyanate polyurea were prepared according to a method similar to that of Example 1, except that in the process of preparing the non-isocyanate polyurea, the reaction temperature of the polyetheramine terminated with hydroxyethyl formate at both ends and 1,3-propylenediamine was adjusted to 100°C, and the reaction pressure was adjusted to 8.0 MPa.

[0182] The non-isocyanate polyurea is prepared to obtain a derivative product of the non-isocyanate polyurea.

[0183] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0184] Comparative Example 2

[0185] A non-isocyanate polyurea and a derivative product of the non-isocyanate polyurea were prepared according to a method similar to that of preparing the non-isocyanate polyurea in Example 1, except that in the process of preparing the water-based non-isocyanate polyurea, the amount of emulsifier added was reduced to 1%.

[0186] The non-isocyanate polyurea is prepared to obtain a derivative product of the non-isocyanate polyurea.

[0187] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0188] Comparative Example 3

[0189] A non-isocyanate polyurea was prepared in exactly the same manner as in Example 3 and further a water-based non-isocyanate polyurea was prepared.

[0190] 39.0 parts by weight of the above-mentioned non-isocyanate polyurea, 42.0 parts by weight of rutile titanium dioxide R105, 1.5 parts by weight of dispersant RHEOBYK 111, and 0.8 parts by weight of defoamer BYK-1790 were mixed and dispersed at a high speed of 1000 r / min for 1 hour; then 0.2 parts by weight of leveling agent (RHEOBYK-410), 0.5 parts by weight of ultraviolet absorber RIASORB UV-928 and 16 parts by weight of diethyl carbonate were added, and dispersed at 500 r / min for 15 minutes to obtain a one-component non-isocyanate polyurea anticorrosive coating.

[0191] 44 parts by weight of the above-mentioned non-isocyanate polyurea, 23 parts by weight of dioctyl phthalate, 25 parts by weight of talc, and 0.5 parts by weight of defoamer BYK-1799 are mixed and dispersed at a high speed of 1000 r / min for 1 hour and at a high speed of 1500 r / min for 1 hour; then 7.5 parts by weight of propylene glycol methyl ether acetate are added and dispersed evenly to obtain a one-component non-isocyanate polyurea waterproof coating.

[0192] 25 parts by weight of the above-mentioned water-based non-isocyanate polyurea, 0.5 parts by weight of defoamer BYK-8821, 0.8 parts by weight of dispersant RHEOBYK 111, 0.2 parts by weight of pH regulator BS 168, 23 parts by weight of rutile titanium dioxide R105, 8 parts by weight of melamine, 11 parts by weight of pentaerythritol, 26 parts by weight of ammonium polyphosphate Exolit AP 422, 0.3 parts by weight of thickener RHEOBYK 420 and 5.2 parts by weight of water were dispersed at a speed of 800 r / min for 1 hour to obtain a water-based non-isocyanate polyurea-based intumescent fire retardant coating.

[0193] According to the measurement method described in detail above, the relevant properties of non-isocyanate polyurea, water-based non-isocyanate polyurea, one-component non-isocyanate polyurea anti-corrosion coating, one-component non-isocyanate polyurea waterproof coating and water-based non-isocyanate polyurea-based intumescent fire retardant coating were tested, and the results are shown in the following Tables 1 and 2.

[0194] Table 1 Performance test results of non-isocyanate polyurea and water-based non-isocyanate polyurea prepared in Examples 1-6 and Comparative Examples 1-3

[0195]

[0196] Table 2 Performance test results of non-isocyanate polyurea anticorrosive coatings, non-isocyanate polyurea waterproof coatings, and water-based non-isocyanate polyurea-based intumescent fire retardant coatings prepared in Examples 1-6 and Comparative Examples 1-3

[0197]

[0198] The above Examples 1-6 demonstrate that the non-isocyanate polyurea, water-based non-isocyanate polyurea, and non-isocyanate polyurea waterproof coatings prepared by the method of the present invention have good mechanical properties (such as tensile strength, tear strength, and elongation at break); the prepared non-isocyanate polyurea anticorrosive coating has high corrosion resistance, and the water-based non-isocyanate polyurea intumescent fire retardant coating has high fire resistance, long service life (water resistance), and good adhesion.

[0199] By comparing the results of Example 1 and Comparative Example 1 in Table 1, it can be seen that when the reaction temperature of the polyetheramine terminated with hydroxyethyl formate at both ends and 1,3-propylenediamine is adjusted to 100°C and the reaction pressure is adjusted to 8.0 MPa in the process of preparing the non-isocyanate polyurea, the physical properties of the product non-isocyanate polyurea are inferior to those of the product of Example 1, and the performance of its derivative products cannot be guaranteed to be at a good level at the same time.

[0200] By comparing the results of Example 1 and Comparative Example 2 in Table 1, it can be seen that when the amount of emulsifier added is less than 3% (i.e., 1% in Comparative Example 2) during the preparation of water-based non-isocyanate polyurea, the physical properties of the product water-based non-isocyanate polyurea will be inferior to those of the product of Example 1, and multiple properties of the water-based non-isocyanate polyurea fire retardant coating will be lower than the average level.

[0201] By comparing the results of Example 3 and Comparative Example 3 in Table 2, it can be seen that the weight ratio of the non-isocyanate polyurea resin in the coating has an important influence on the performance of the obtained non-isocyanate polyurea anticorrosive coating. The non-isocyanate polyurea anticorrosive coating prepared by deviating from 50-80 parts by weight of the non-isocyanate polyurea (i.e., as shown in Comparative Example 3, the weight percentage of the non-isocyanate polyurea is 39 weight%) will result in the inability to simultaneously achieve good anticorrosion performance.

[0202] The embodiments described in the present invention are merely descriptions of the preferred implementation modes of the present invention, and are not intended to limit the concept and scope of the present invention. Without departing from the design concept of the present invention, various modifications and improvements made to the technical solutions of the present invention by engineers and technicians in this field should fall within the protection scope of the present invention. The technical contents for which protection is sought in the present invention have all been recorded in the claims.

Claims

1. A non-isocyanate polyurea having a structure represented by the following general formula (1): General formula (1) in, R1 is a divalent residue obtained by removing two amino groups from a polyetheramine, which is an amino-terminated polyoxypropylenediamine having a number average molecular weight in the range of 230 to 5000; R2 is a C2-C8 divalent aliphatic group or a divalent alicyclic group; and n is an integer of 30-300.

2. The non-isocyanate polyurea according to claim 1, wherein the polyetheramine is an amino-terminated polyoxypropylene diamine having a number average molecular weight in the range of 400 to 2000.

3. The non-isocyanate polyurea according to claim 1, wherein R2 is a C2-C8 divalent straight-chain aliphatic group.

4. The non-isocyanate polyurea according to claim 1, wherein n is an integer of 80-200.

5. A method for preparing a non-isocyanate polyurea according to any one of claims 1 to 4, comprising the following steps: (1) mixing ethylene carbonate and polyetheramine and heating them to react to obtain a polyetheramine capped at both ends with hydroxyethyl formate; (2) adding a C2-C8 aliphatic diamine and a catalyst to the polyetheramine end-capped with hydroxyethyl formate at both ends, mixing them evenly and heating them, reacting them under high pressure, and removing ethylene glycol by distillation under reduced pressure after the reaction is completed; and (3) cooling the product obtained in step (2) and slowly adding a first organic solvent thereto to obtain the non-isocyanate polyurea.

6. The method for preparing a non-isocyanate polyurea according to claim 5, wherein the C2-C8 aliphatic diamine is selected from one or more of ethylenediamine, 1,2-propylenediamine, N-ethylethylenediamine, 1,4-butylenediamine, 1,3-cyclohexyldimethylamine, 1,3-propylenediamine, 1,5-pentanediamine, hexamethylenediamine, 2-methyl-1,3-propylenediamine, 2-methylpentanediamine and cyclohexanediamine.

7. The method for preparing non-isocyanate polyurea according to claim 5, wherein the catalyst is an organic nitrogen heterocyclic compound.

8. The method for preparing non-isocyanate polyurea according to claim 5, wherein the catalyst is selected from one or more of pyridine compounds, pyran compounds, quinoline compounds and pyrimidine compounds.

9. The method for preparing a non-isocyanate polyurea according to claim 5, wherein the catalyst is selected from 2,3-dihydroxypyridine, 4,6-dimethylpyrimidine, 4-hydroxymethylpyrimidine, 3-hydroxy-6-methylpyridine, 4-benzylpyridine, tetrahydropyran, 3,4-dihydro-2H-pyran, 4-hydroxy-6-methyl-2-pyrone, N-methyltetrahydro-2H-pyran-4-amine, 7-hydroxyisoquinoline, 4-hydroxy-2-methylindole, One or more of 1-methylisoquinoline, 6,7-dihydro-5H-quinolin-8-one, 1,2,3,4-tetrahydroquinoline, 3,4-dihydro-7-hydroxy-2(1H)-quinolinone, 4-hydroxy-N-methyl-2-quinoline, 3-phenyl-4-[3H]quinazolinone, 5-methylpyrimidine, 2,4-dimethoxypyrimidine, 2,4,6-trimethoxypyrimidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

10. The method for preparing non-isocyanate polyurea according to claim 5, wherein the first organic solvent is selected from one or more of xylene, cyclohexane, acetone, cyclohexanone and dichloromethane.

11. The method for preparing a non-isocyanate polyurea according to claim 5, wherein in step (1), the molar ratio of the ethylene carbonate to the polyetheramine is 1.8:1 to 2:

1.

12. The method for preparing non-isocyanate polyurea according to claim 5, wherein in step (1), the reaction temperature is 90-120°C and the reaction time is 9-15h.

13. The method for preparing non-isocyanate polyurea according to claim 5, wherein in step (2), the molar ratio of the polyetheramine end-capped with hydroxyethyl formate at both ends to the C2-C8 aliphatic diamine is 1:1 to 1:1.

2.

14. The method for preparing non-isocyanate polyurea according to claim 5, wherein in step (2), the weight ratio of the catalyst to the aliphatic diamine is 1×10 -6 : 1 to 1×10 -3 :

1.

15. The method for preparing non-isocyanate polyurea according to claim 5, wherein in step (2), the reaction temperature is 120-200°C, the reaction pressure is 15-20 MPa, and the reaction time is 12-24 hours.

16. A method for preparing a water-based non-isocyanate polyurea, the method comprising the following steps: (1) slowly adding a second organic solvent to the non-isocyanate polyurea according to any one of claims 1 to 4 and stirring uniformly; (2) adding an emulsifier and water to the product prepared in step (1) under high-speed dispersion, and removing the second organic solvent by reduced pressure distillation to obtain the water-based non-isocyanate polyurea.

17. The method for preparing an aqueous non-isocyanate polyurea according to claim 16, wherein the second organic solvent is ethyl acetate.

18. The method for preparing an aqueous non-isocyanate polyurea according to claim 16, wherein the emulsifier is selected from one or more of sodium lauryl sulfate, phenol ethylene oxide and phenol ethylene oxide.

19. The method for preparing water-based non-isocyanate polyurea according to claim 16, wherein the amount of the emulsifier added is 2-10% by weight based on 100% by weight of the non-isocyanate polyurea.

20. The method for preparing a water-based non-isocyanate polyurea according to claim 16, wherein the ratio of the weight of the non-isocyanate polyurea to the weight of the added water is in the range of 1:1 to 1:

5.

21. A one-component non-isocyanate polyurea anti-corrosion coating, comprising: 50-80 parts by weight of the non-isocyanate polyurea according to any one of claims 1 to 4, 10-30 parts by weight of rutile titanium dioxide, 0.5-1.5 parts by weight of a dispersant, 0.5-0.8 parts by weight of a defoamer, 0.1-0.3 parts by weight of a leveling agent, 0.3-0.6 parts by weight of an ultraviolet absorber and 2-20 parts by weight of a third organic solvent.

22. The one-component non-isocyanate polyurea anticorrosive coating according to claim 21, wherein: The dispersant is an anionic wetting dispersant; and / or The defoamer is a polyolefin solution defoamer; and / or The leveling agent is selected from one or more of an organic silicon leveling agent and a modified acrylic leveling agent; and / or The ultraviolet absorber is selected from one or more of benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, benzotriazole ultraviolet absorbers, substituted acrylonitrile ultraviolet absorbers and triazine ultraviolet absorbers; and / or The third organic solvent is selected from one or more of butyl acetate, diethyl carbonate, propylene glycol methyl ether acetate and xylene.

23. A one-component non-isocyanate polyurea waterproof coating, the one-component non-isocyanate polyurea waterproof coating comprising: 25-50 parts by weight of the non-isocyanate polyurea according to any one of claims 1 to 4, 15-30 parts by weight of a plasticizer, 20-30 parts by weight of a filler, 0.1-0.5 parts by weight of a defoamer and 3-10 parts by weight of a fourth organic solvent.

24. The one-component non-isocyanate polyurea waterproof coating according to claim 23, wherein: The plasticizer is selected from one or more of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, trioctyl phosphate, citrate, and chlorinated paraffin plasticizers; and / or The filler is selected from one or more of rutile titanium dioxide, kaolin, heavy calcium, barium sulfate, magnesium oxide, calcium oxide, wollastonite, and talc; and / or The defoamer is a polyolefin solution defoamer; and / or The fourth organic solvent is selected from one or more of xylene, solvent oil, ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.

25. A water-based non-isocyanate polyurea-based intumescent fire-retardant coating, comprising: 25-40 parts by weight of water-based non-isocyanate polyurea prepared by the preparation method according to any one of claims 16 to 20, 0.1-0.5 parts by weight of a defoamer, 0.5-1.2 parts by weight of a dispersant, 0.1-0.5 parts by weight of a pH regulator, 20-30 parts by weight of rutile titanium dioxide, 6-15 parts by weight of melamine, 6-15 parts by weight of pentaerythritol, 20-30 parts by weight of ammonium polyphosphate, 0.3-1 parts by weight of a thickener and 10-25 parts by weight of water.

26. The water-based non-isocyanate polyurea-based intumescent fire retardant coating according to claim 25, wherein: The defoamer is selected from one or more of a mineral oil defoamer and a polyether-modified silicone defoamer; and / or The dispersant is an anionic wetting dispersant; and / or The pH regulator is an aqueous solution of reactive organosilicon; and / or The thickener is a polyurethane modified polyether associative thickener.

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