Metallocene modified amino-terminated polyether and polyurea resin, and preparation method and application thereof

Abstract

The invention relates to the technical field of functional materials, and discloses metallocene modified amino-terminated polyether and polyurea resin as well as a preparation method and application thereof. The metallocene modified amino-terminated polyether is obtained by modifying first amino-terminated polyether through metallocene; wherein the metal in the metallocene modified amino-terminated polyether is a transition metal, and the weight-average molecular weight of the first amino-terminated polyether is 400 to 2000. The polyurea resin prepared from the metallocene modified amino-terminated polyether has good mechanical properties, flame retardancy, aging resistance and storage stability.

Description

Technical Field

[0001] This invention relates to the field of functional materials technology, specifically to a metallocene-modified amino-terminated polyether and polyurea resin, their preparation methods, and applications. Background Technology

[0002] Many existing buildings in the petrochemical industry and military sectors, due to their age and lack of blast resistance design, no longer meet current standards and require blast-resistant reinforcement in areas prone to explosions. Traditional methods include point reinforcement and external steel reinforcement, but these methods are difficult to implement, time-consuming, and costly to modify. Sprayed polyurea elastomers offer advantages such as rapid curing, insensitivity to moisture, environmental friendliness, and excellent physical and chemical properties, leading to their widespread application in waterproofing and corrosion protection. However, ordinary polyurea materials have two drawbacks: firstly, their low mechanical properties fail to meet blast-resistant requirements; secondly, polyurea is highly flammable, with a limiting oxygen index (LOI) of less than 20%, which does not meet the requirements for building retrofit applications. Therefore, developing flame-retardant sprayed blast-resistant polyurea materials is essential for the blast-resistant reinforcement of existing buildings. However, current flame-retardant modification technologies for polyurea mainly rely on adding flame retardants, which inevitably reduces mechanical properties, making it difficult for polyurea materials to meet blast-resistant requirements. In addition, there are problems such as easy precipitation, low flame retardant efficiency, poor compatibility, and poor thermal stability. Summary of the Invention

[0003] The purpose of this invention is to overcome the problems existing in the prior art and provide a metallocene-modified amino-terminated polyether. The polyurea resin prepared using this metallocene-modified amino-terminated polyether has good mechanical properties, flame retardant properties, aging resistance and storage stability.

[0004] To achieve the above objectives, the present invention provides a metallocene-modified amino-terminated polyether, wherein the metallocene-modified amino-terminated polyether is obtained by modifying a first amino-terminated polyether with metallocene.

[0005] The metal in the metallocene-modified amino-terminated polyether is a transition metal, and the weight-average molecular weight of the first amino-terminated polyether is 400-2000.

[0006] Preferably, the metal in the metallocerocene-modified amino-terminated polyether is selected from chromium, manganese, vanadium, iron, cobalt, or nickel.

[0007] Preferably, the weight-average molecular weight of the metallocene-modified amino-terminated polyether is 500-3000.

[0008] A second aspect of the present invention provides a method for preparing the above-mentioned metallocene-modified amino-terminated polyether, the method comprising:

[0009] In the presence of a first organic solvent, the first terminal amino polyether and 1,1'-dichlorocarbonyl dimetallocene are subjected to a first reaction.

[0010] Preferably, the first organic solvent is selected from one or more of toluene, xylene, N,N-dimethylformamide and dimethyl sulfoxide.

[0011] Preferably, the weight ratio of the first terminal amino polyether to the 1,1'-dichlorocarbonyl dimetallocene is 2-2.4:1.

[0012] Preferably, the conditions for the first reaction include: a temperature of 10-40°C and a time of 10-60 min.

[0013] A third aspect of the present invention provides a composition for use with polyurea resin, the composition comprising a prepolymer, a second-terminated amino polyether, a chain extender, a metallocene-modified amino polyether, and a compounded flame retardant;

[0014] The isocyanate index of the polyurea resin composition is 1-1.1.

[0015] The prepolymer is obtained by polymerization of isocyanate, second polyether polyol, metallocene-modified polyether polyol and polycarbonate diol;

[0016] The metallocene-modified polyether polyol is obtained by modifying the first polyether polyol with metallocene; the metal in the metallocene-modified polyether polyol is a transition metal, and the weight-average molecular weight of the first polyether polyol is 400-800.

[0017] The metallocene-modified amino-terminated polyether is the aforementioned metallocene-modified amino-terminated polyether.

[0018] The compound flame retardant comprises triethyl phosphate, zinc borate, and a charring agent.

[0019] Preferably, the viscosity of the prepolymer is 1500-3000 mPa·s.

[0020] Preferably, based on the total weight of the isocyanate, second polyether polyol, metallocene-modified polyether polyol, and polycarbonate diol used to prepare the prepolymer, the content of the isocyanate is 40-70 wt%, the content of the second polyether polyol is 10-40 wt%, the content of the metallocene-modified polyether polyol is 5-20 wt%, and the content of the polycarbonate diol is 1-20 wt%.

[0021] Preferably, the method for preparing the prepolymer includes the following steps:

[0022] A1: Mix the second polyether polyol and polycarbonate diol and heat to 100℃-130℃. Dehydrate under vacuum and determine the water content to be ≤0.05wt%. Then release the vacuum for later use.

[0023] A2: Mix the metallocene-modified polyether polyol with isocyanate, then mix it with the intermediate material obtained in step A1 under a protective atmosphere to react, and then perform solid-liquid separation to obtain the prepolymer.

[0024] Preferably, in step A2, the reaction conditions include: a temperature of 75-90°C and a time of 2-4 hours.

[0025] Preferably, the second polyether polyol is selected from one or more of polyether polyol DL1000, polyether polyol Y1030 and polyether polyol 1000LM.

[0026] Preferably, the isocyanate is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, phenylmethylene diisocyanate and lysine diisocyanate.

[0027] Preferably, the weight-average molecular weight of the metallocene-modified polyether polyol is 500-2000.

[0028] Preferably, the preparation method of the metallocene-modified polyether polyol includes:

[0029] In the presence of a second organic solvent, the first polyether polyol and 1,1'-dichlorocarbonyl dimetallocene undergo a second reaction.

[0030] Preferably, the second organic solvent is selected from one or more of toluene, xylene, N,N-dimethylformamide and dimethyl sulfoxide.

[0031] Preferably, the molar ratio of the first polyether polyol to the 1,1'-dichlorocarbonyl dimetallocene is 2-2.4:1.

[0032] Preferably, the conditions for the second reaction include: a temperature of 60-100°C and a time of 1-5 hours.

[0033] Preferably, the polyurea resin composition further contains an additive selected from one or more of anti-settling agents, coupling agents, and molecular sieves.

[0034] Preferably, based on the total weight of the second-terminated amino polyether, chain extender, metallocene-modified amino polyether, compound flame retardant, and optional additives, the content of the second-terminated amino polyether is 10-60 wt%, the content of the chain extender is 10-60 wt%, the content of the metallocene-modified amino polyether is 5-30 wt%, the content of the compound flame retardant is 10-25 wt%, and the content of the additives is 0-1.5 wt%.

[0035] Preferably, the second amino-terminated polyether is selected from one or more of amino-terminated polyether D2000, amino-terminated polyether T5000, amino-terminated polyether D400 and amino-terminated polyether T403.

[0036] Preferably, the chain extender is selected from one or more of diethyltoluenediamine, dimethylthiotoluenediamine, N,N′-dialkyldiamine, 1,4-bis-sec-butylaminobenzene, 4,4′-bis-sec-methylaminodiphenylmethane, and N,N′-bis-sec-pentylcyclohexanediamine.

[0037] The additives are selected from one or more of coupling agents, defoamers, and molecular sieves.

[0038] Preferably, based on the total weight of the compound flame retardant, the content of triethyl phosphate is 50-80 wt%, the content of zinc borate is 10-25 wt%, and the content of charring agent is 10-35 wt%.

[0039] Preferably, the charring agent is selected from one or more of pentaerythritol, dipentaerythritol, sorbitol, and Sanqin charring agent HF-T1020.

[0040] A fourth aspect of the present invention provides a method for preparing a polyurea resin, the method comprising: mixing the components of the above-mentioned polyurea resin composition.

[0041] The fifth aspect of the present invention provides a polyurea resin prepared by the above method.

[0042] The sixth aspect of the present invention provides a method for preparing a polyurea resin coating, the method comprising: spraying the above-mentioned polyurea resin onto a substrate and then curing it.

[0043] Preferably, the environmental conditions for spraying include: an ambient temperature of 20-25°C and an ambient relative humidity of 45-75%.

[0044] Preferably, the spraying conditions include: a temperature of ≥65℃ and a dynamic pressure of >13.8MPa.

[0045] Preferably, the curing conditions include a temperature of 15-40℃ and a time of ≥7 days.

[0046] Preferably, the thickness of the polyurea resin coating obtained after curing is 2-10 mm.

[0047] The seventh aspect of the present invention provides the application of the above-described polyurea resin in explosion-proof materials.

[0048] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0049] The polyurea resin of this invention possesses excellent mechanical properties, flame retardant properties, aging resistance, and storage stability. This is mainly due to the fact that the compounded flame retardant contains flame retardant elements and charring agents, while the raw materials for preparing the prepolymer contain metallocene-modified polyether polyol and isocyanate. The metallocene contained therein can promote char formation under the action of air. At the same time, the synergistic flame retardant effect of phosphorus in the compounded flame retardant and metallocene in the metallocene-modified amino-terminated polyether results in the polyurea resin of this invention possessing both excellent mechanical and flame retardant properties. Furthermore, the prepolymer contained in the polyurea resin of this invention is prepared using metallocene-modified polyether polyol, and the polyurea resin of this invention also contains metallocene-modified amino-terminated polyether. Therefore, the polyurea resin of this invention has excellent aging resistance and good storage stability. Detailed Implementation

[0050] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0051] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0052] In one aspect, the present invention provides a metallocene-modified amino-terminated polyether, wherein the metallocene-modified amino-terminated polyether is obtained by modifying a first amino-terminated polyether with metallocene.

[0053] The metal in the metallocene-modified amino-terminated polyether is a transition metal, and the weight-average molecular weight of the first amino-terminated polyether is 400-2000.

[0054] In a preferred embodiment, the metal in the metallocerocene-modified amino-terminated polyether is selected from chromium, manganese, vanadium, iron, cobalt, or nickel.

[0055] In a preferred embodiment, the metallocene-modified amino-terminated polyether has a weight-average molecular weight of 500-3000.

[0056] A second aspect of the present invention provides a method for preparing the above-mentioned metallocene-modified amino-terminated polyether, the method comprising:

[0057] In the presence of a first organic solvent, the first terminal amino polyether and 1,1'-dichlorocarbonyl dimetallocene are subjected to a first reaction.

[0058] In a preferred embodiment, the 1,1'-dichlorocarbonyl dicerocene used to prepare the metallocene-modified amino-terminated polyether is selected from 1,1'-dichlorocarbonyl chromium dicerocene, 1,1'-dichlorocarbonyl manganese dicerocene, 1,1'-dichlorocarbonyl vanadium dicerocene, 1,1'-dichlorocarbonyl ferrocene, 1,1'-dichlorocarbonyl cobalt dicerocene, or 1,1'-dichlorocarbonyl nickel dicerocene.

[0059] In a preferred embodiment, the first organic solvent is selected from one or more of toluene, xylene, N,N-dimethylformamide and dimethyl sulfoxide.

[0060] In this invention, there are no special requirements for the amount of the first organic solvent, as long as it can dissolve 1,1'-dichlorocarbonyl metallocene.

[0061] In this invention, the first reaction for preparing the above-mentioned metallocene-modified amino-terminated polyether is carried out under alkaline conditions; in a preferred embodiment, the first reaction is carried out under conditions with a pH of 7-10.

[0062] In this invention, there are no special requirements for the substance used to adjust the pH value during the first reaction process, as long as the pH value can be adjusted to 7-10; for example, the substance can be one or more of sodium hydroxide solution, sodium bicarbonate solution and pyridine.

[0063] In a preferred embodiment, in order to improve reaction efficiency and increase yield, the molar ratio of the first terminal amino polyether to the 1,1'-dichlorocarbonyl dimetallocene is 2-2.4:1; preferably 2-2.2:1.

[0064] In a preferred embodiment, the first amino-terminated polyether is polyoxypropylene diamine and / or amino-terminated trimethylolpropane tripropylene glycol ether; specifically, the polyoxypropylene diamine can be polyoxypropylene diamine D400 or polyoxypropylene diamine D2000.

[0065] In a preferred embodiment, the conditions for the first reaction include: a temperature of 10-40°C and a time of 10-60 min.

[0066] In this invention, the first reaction is carried out under a protective atmosphere, which is selected from a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, or an argon atmosphere.

[0067] In a preferred embodiment, the method for preparing the above-mentioned metallocene-modified amino-terminated polyether further includes solid-liquid separation, drying, and washing of the material after the first reaction.

[0068] In this invention, there are no special requirements for the method of solid-liquid separation; any method conventionally applicable in the art is acceptable, such as filtration.

[0069] In one specific embodiment, the process for preparing the above-mentioned metallocene-modified amino-terminated polyether includes: dissolving 1,1'-dichlorocarbonyl metallocene (e.g., 1,1'-dichlorocarbonyl ferrocene) in a first organic solvent (e.g., toluene), then adding a first amino-terminated polyether (e.g., polyoxypropylene diamine D400) under a protective atmosphere (e.g., nitrogen atmosphere) to obtain a mixture, adjusting the pH of the mixture to 7-10 using an alkaline solution (e.g., 6.25 wt% sodium hydroxide solution), stirring at room temperature (e.g., 20°C) to carry out a first reaction, then performing solid-liquid separation (e.g., filtration) on the material after the first reaction, and washing and drying the obtained liquid phase material.

[0070] A third aspect of the present invention provides a composition for use with polyurea resin, the composition comprising a prepolymer, a second-terminated amino polyether, a chain extender, a metallocene-modified amino polyether, and a compounded flame retardant;

[0071] The isocyanate index of the polyurea resin composition is 1-1.1.

[0072] The prepolymer is obtained by polymerization of isocyanate, second polyether polyol, metallocene-modified polyether polyol and polycarbonate diol;

[0073] The metallocene-modified polyether polyol is obtained by modifying the first polyether polyol with metallocene; the metal in the metallocene-modified polyether polyol is a transition metal, and the weight-average molecular weight of the first polyether polyol is 400-800.

[0074] The metallocene-modified amino-terminated polyether is the aforementioned metallocene-modified amino-terminated polyether.

[0075] The compound flame retardant comprises triethyl phosphate, zinc borate, and a charring agent.

[0076] In this invention, the "isocyanate index" refers to the molar ratio of isocyanate groups to hydroxyl and amino groups in the polyurea resin composition system.

[0077] In a preferred embodiment, in order to improve the thermal stability of the prepolymer, the viscosity of the prepolymer is 1500-3000 mPa·s; preferably 1600-2500 mPa·s; specifically, the viscosity of the prepolymer can be 1600 mPa·s, 1700 mPa·s, 1800 mPa·s, 1900 mPa·s, 2000 mPa·s, 2100 mPa·s, 2200 mPa·s, 2300 mPa·s, 2400 mPa·s, or 2500 mPa·s.

[0078] In a preferred embodiment, to further improve the thermal stability of the prepolymer, based on the total weight of the isocyanate, second polyether polyol, metallocene-modified polyether polyol, and polycarbonate diol used to prepare the prepolymer, the content of the isocyanate is 40-70 wt%, the content of the second polyether polyol is 10-40 wt%, the content of the metallocene-modified polyether polyol is 5-20 wt%, and the content of the polycarbonate diol is 1-20 wt%; preferably, the content of the isocyanate is 55-70 wt%, the content of the second polyether polyol is 10-25 wt%, the content of the metallocene-modified polyether polyol is 5-15 wt%, and the content of the polycarbonate diol is 5-20 wt%.

[0079] In specific embodiments, the content of the isocyanate can be 55wt%, 60wt%, 65wt%, or 70wt%; the content of the second polyether polyol can be 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, or 25wt%; the content of the metallocene-modified polyether polyol can be 5wt%, 8wt%, 10wt%, 12wt%, or 15wt%; and the content of the polycarbonate diol can be 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, or 20wt%.

[0080] In a preferred embodiment, the method for preparing the prepolymer includes the following steps:

[0081] A1: Mix the second polyether polyol and polycarbonate diol and heat to 100℃-130℃. Dehydrate under vacuum and determine the water content to be ≤0.05wt%. Then release the vacuum for later use.

[0082] A2: Mix the metallocene-modified polyether polyol with isocyanate, then mix it with the intermediate material obtained in step A1 under a protective atmosphere to react, and then perform solid-liquid separation to obtain the prepolymer.

[0083] In this invention, in step A2, the protective atmosphere is selected from nitrogen atmosphere, helium atmosphere, neon atmosphere or argon atmosphere.

[0084] In this invention, there are no special requirements for the dehydration time in step A1, as long as the water content of the dehydrated substance is ≤0.05wt%. In a preferred embodiment, the dehydration time is 2-3 hours.

[0085] In a preferred embodiment, in step A1, the vacuum conditions include a pressure of -0.1 to 0.07 MPa.

[0086] In a preferred embodiment, the reaction conditions in step A2 include a temperature of 75-90°C and a time of 2-4 hours.

[0087] In a preferred embodiment, the second polyether polyol is selected from one or more of polyether polyol DL1000, polyether polyol Y1030, and polyether polyol 1000LM.

[0088] In a preferred embodiment, the polycarbonate diol is selected from one or more of Tosoh 981, Desmophen C1100, and Desmophen C1200.

[0089] In a preferred embodiment, the isocyanate is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, phenylmethylene diisocyanate, and lysine diisocyanate.

[0090] In a preferred embodiment, the weight-average molecular weight of the metallocene-modified polyether polyol is 500-2000.

[0091] In a preferred embodiment, the preparation method of the metallocene-modified polyether polyol includes:

[0092] In the presence of a second organic solvent, the first polyether polyol and 1,1'-dichlorocarbonyl dimetallocene undergo a second reaction.

[0093] In a preferred embodiment, the 1,1'-dichlorocarbonyldicyclopentene used to prepare the metallocene-modified polyether polyol is selected from 1,1'-dichlorocarbonylchromium, 1,1'-dichlorocarbonylmanganese, 1,1'-dichlorocarbonylvanadium, 1,1'-dichlorocarbonylferrocene, 1,1'-dichlorocarbonylcobalt, or 1,1'-dichlorocarbonylnickel. In a preferred embodiment, the second organic solvent is selected from one or more of toluene, xylene, N,N-dimethylformamide, and dimethyl sulfoxide.

[0094] In this invention, there are no special requirements for the amount of the second organic solvent used, as long as it can dissolve 1,1'-dichlorocarbonyl dimetallocene.

[0095] In this invention, the second reaction for preparing the above-mentioned metallocene-modified polyether polyol is carried out under alkaline conditions; in a preferred embodiment, the second reaction is carried out under conditions with a pH of 7-10.

[0096] In this invention, there are no special requirements for the substance used to adjust the pH value during the second reaction process, as long as the pH value can be adjusted to 7-10; for example, the substance can be one or more of sodium hydroxide solution, sodium bicarbonate solution and pyridine.

[0097] In a preferred embodiment, in order to improve reaction efficiency and increase yield, the molar ratio of the first polyether polyol and the 1,1'-dichlorocarbonyl dimetallocene is 2-2.4:1; preferably 2-2.2:1.

[0098] In a preferred embodiment, the first polyether polyol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol, and polytetrahydrofuran ether glycol; specifically, the polyethylene oxide glycol can be polyethylene oxide glycol PEG600, the polypropylene oxide glycol can be polypropylene oxide glycol PPG600, and the polytetrahydrofuran ether glycol can be polytetrahydrofuran ether glycol PTMG650.

[0099] In a preferred embodiment, the conditions for the second reaction include: a temperature of 60-100°C and a time of 1-5 hours; preferably, a temperature of 70-90°C and a time of 3-5 hours; specifically, the temperature can be 70°C, 75°C, 80°C, 85°C, or 90°C; and the time can be 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours.

[0100] In this invention, the second reaction is carried out under a protective atmosphere selected from nitrogen, helium, neon or argon atmosphere.

[0101] In a preferred embodiment, the method for preparing the above-mentioned metallocene-modified polyether polyol further includes solid-liquid separation and purification of the material after the first reaction.

[0102] In this invention, there are no special requirements for the solid-liquid separation and purification methods; any method conventionally applicable in the art is acceptable. For example, the solid-liquid separation method can be filtration, and the purification method can be concentration and extraction. Preferably, the extraction solvent is dichloromethane.

[0103] In one specific embodiment, the method for preparing the above-mentioned metallocene-modified polyether polyol includes: dissolving 1,1'-dichlorocarbonyl metallocene (e.g., 1,1'-dichlorocarbonyl ferrocene) in an organic solvent (e.g., toluene), then adding a first polyether polyol (e.g., polyethylene oxide glycol PEG600) under a protective atmosphere (e.g., nitrogen atmosphere) to obtain a mixture, adjusting the pH of the mixture to 7-10 using an alkaline solution (e.g., pyridine), stirring the mixture at room temperature (e.g., 20°C), performing solid-liquid separation (e.g., filtration) on the material obtained after the reaction, concentrating the obtained intermediate liquid phase material, extracting the concentrated material using an extraction solvent (e.g., dichloromethane), washing with water, and then drying and concentrating the obtained organic layer to obtain the metallocene-modified polyether polyol.

[0104] In a preferred embodiment, the polyurea resin composition further comprises an additive selected from one or more of antisettling agents, coupling agents, and molecular sieves.

[0105] In a specific implementation, the coupling agent is Momentive A-187 silane coupling agent.

[0106] In a specific embodiment, the defoamer is BYK A535 silicone defoamer.

[0107] In a preferred embodiment, to further improve the explosion-proof and flame-retardant properties of the polyurea resin coating prepared by the polyurea resin composition, based on the total weight of the second-terminated amino polyether, chain extender, metallocene-modified terminal amino polyether, compound flame retardant, and optional additives, the content of the second-terminated amino polyether is 10-60 wt%, the content of the chain extender is 10-60 wt%, the content of the metallocene-modified terminal amino polyether is 5-30 wt%, the content of the compound flame retardant is 10-25 wt%, and the content of the additives is 0-1.5 wt%. Preferably, the content of the second-terminated amino polyether is 25-60 wt%, the content of the chain extender is 10-40 wt%, the content of the metallocene-modified terminal amino polyether is 10-20 wt%, the content of the compound flame retardant is 10-20 wt%, and the content of the additives is 0.3-1.5 wt%.

[0108] In specific embodiments, the content of the second terminal amino polyether can be 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, or 60wt%; the content of the chain extender can be 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, or 40wt%; the content of the metallocene-modified terminal amino polyether can be 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt%, or 20wt%; the content of the compounded flame retardant can be 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt%, or 20wt%; and the content of the additives can be 0.3wt%, 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, or 1.5wt%.

[0109] In a preferred embodiment, the second amino-terminated polyether is selected from one or more of amino-terminated polyether D2000, amino-terminated polyether T5000, amino-terminated polyether D400, and amino-terminated polyether T403.

[0110] In a preferred embodiment, the chain extender is selected from one or more of diethyltoluenediamine, dimethylthiotoluenediamine, N,N′-dialkyldiamine, 1,4-bis-sec-butylaminobenzene, 4,4′-bis-sec-methylaminodiphenylmethane, and N,N′-bis-sec-pentylcyclohexanediamine.

[0111] In a preferred embodiment, to further improve the flame retardant properties of the polyurea resin coating prepared by the polyurea resin composition, based on the total weight of the compounded flame retardants, the content of triethyl phosphate is 50-80 wt%, the content of zinc borate is 10-25 wt%, and the content of the charring agent is 10-35 wt%; preferably, the content of triethyl phosphate is 50-65 wt%, the content of zinc borate is 15-25 wt%, and the content of the charring agent is 15-25 wt%.

[0112] In a specific embodiment, the content of triethyl phosphate can be 50 wt%, 55 wt%, 60 wt%, or 65 wt%; the content of zinc borate can be 15 wt%, 18 wt%, 20 wt%, 22 wt%, or 25 wt%; and the content of the charring agent can be 15 wt%, 18 wt%, 20 wt%, 22 wt%, or 25 wt%.

[0113] In a preferred embodiment, the charring agent is selected from one or more of pentaerythritol, dipentaerythritol, sorbitol, and Sanqin charring agent HF-T1020.

[0114] A fourth aspect of the present invention provides a method for preparing a polyurea resin, the method comprising: mixing the components of the above-mentioned polyurea resin composition.

[0115] In a preferred embodiment, the method for preparing polyurea resin specifically includes the following steps: mixing and filtering the polyurea resin with all components in the composition except the prepolymer for 1 hour, and then mixing the filtered filtrate with the prepolymer.

[0116] The fifth aspect of the present invention provides a polyurea resin prepared by the above method.

[0117] The sixth aspect of the present invention provides a method for preparing a polyurea resin coating, the method comprising: spraying the above-mentioned polyurea resin onto a substrate and then curing it.

[0118] In a preferred embodiment, in order to improve the overall performance of the polyurea resin coating, the environmental conditions for spraying include: an ambient temperature of 20-25°C and an ambient relative humidity of 45-75%.

[0119] In a preferred embodiment, the spraying conditions include: a temperature ≥65°C and a dynamic pressure >13.8MPa.

[0120] In a preferred embodiment, the curing conditions include a temperature of 15-40°C and a time of ≥7 days.

[0121] In a preferred embodiment, the thickness of the polyurea resin coating obtained after curing is 2-10 mm.

[0122] The polyurea resin of this invention possesses excellent mechanical properties, flame retardant properties, aging resistance, and storage stability. This is mainly due to the fact that the compounded flame retardant contains flame retardant elements and charring agents, while the raw materials for preparing the prepolymer contain metallocene-modified polyether polyol and isocyanate. The metallocene contained therein can promote char formation under the action of air. At the same time, the synergistic flame retardant effect of phosphorus in the compounded flame retardant and metallocene in the metallocene-modified amino-terminated polyether results in the polyurea resin of this invention possessing both excellent mechanical and flame retardant properties. Furthermore, the prepolymer of the polyurea resin of this invention is prepared using metallocene-modified polyether polyol, and the polyurea resin of this invention also contains metallocene-modified amino-terminated polyether. Therefore, the polyurea resin of this invention has excellent aging resistance and good storage stability.

[0123] The seventh aspect of the present invention provides the application of the above-described polyurea resin in explosion-proof materials.

[0124] The following examples further illustrate the metallocene-modified amino-terminated polyether and polyurea resin, their preparation method, and applications according to the present invention. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0125] Unless otherwise specified, the experimental methods used in the following examples are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following examples are commercially available; 1,1'-dichlorocarbonylferrocene, 1,1'-dichlorocarbonylcobaltene, and 1,1'-dichlorocarbonylnickelene were purchased from Antec Chemical Company; polyethylene glycol PEG600, polypropylene glycol PPG600, and polytetrahydrofuran ether glycol PTMG650 were purchased from BASF; Tosoh 981 was purchased from Tosoh Corporation; Desmophen C1100 and Desmophen C1200 were purchased from Covestro AG; polypropylene diamine D400, amino-terminated trimethylolpropane tripropylene glycol ether, and polypropylene diamine... D2000 was purchased from Huntsman Corporation; toluene from Sinopharm Reagent Company; pyridine from Sinopharm Reagent Company; dichloromethane from Sinopharm Reagent Company; polyether polyol DL400 from Dongda Polyurethane Company; diphenyl diisocyanate from Wanhua Chemical Company; amino-terminated polyether D2000 from Huntsman Corporation; diethyltoluene diamine from Xiangyuan New Materials Co., Ltd.; anti-settling agent BYKW-961 from BYK Chemical Co., Ltd.; coupling agent Momentive A-187 silane coupling agent from Momentive Corporation; molecular sieve A3 from Grace Company; triethyl phosphate TEP from Zhangjiagang Yarui Chemical Co., Ltd.; and charring agent pentaerythritol from Xiongda Chemical Co., Ltd.

[0126] Example 1

[0127] Preparation of ferrocene-modified amino-terminated polyether L1:

[0128] 1,1'-Dichlorocarbonylferrocene was dissolved in 700 parts by weight of toluene, and then polyoxypropylene diamine D400 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polyoxypropylene diamine D400 and 1,1'-dichlorocarbonylferrocene was 2.1:1. The pH of the mixture was adjusted to 7.8 using a 6.25 wt% sodium hydroxide solution, and the mixture was stirred at room temperature (20 °C) for 30 min to carry out the first reaction. The resulting intermediate material was then filtered, and the intermediate liquid phase was washed with chloroform and then dried to obtain ferrocene-modified amino-terminated polyether L1 (weight average molecular weight of 1278).

[0129] Preparation of ferrocene-modified polyether polyol S1:

[0130] 1,1'-Dichlorocarbonylferrocene was dissolved in 100 parts by weight of toluene, and then polytetrahydrofuran ether glycol PTMG650 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polytetrahydrofuran ether glycol PTMG650 and 1,1'-dichlorocarbonylferrocene was 2.1:1. The pH of the mixture was adjusted to 8 using 10 parts by weight of pyridine, and the mixture was stirred at 70°C for 4 hours to carry out the second reaction. The obtained intermediate material was then filtered, and the obtained intermediate liquid phase was concentrated. The concentrated material was extracted using dichloromethane as an extraction solvent, and then washed with water. The obtained organic layer was then dried and concentrated again to obtain ferrocene-modified polyether polyol S1 (weight average molecular weight of 1524).

[0131] Preparation of prepolymer K1:

[0132] A1: Mix 20 parts by weight of polyether polyol DL1000 and 10 parts by weight of polycarbonate diol Tosoh981, heat to 120°C, dehydrate under vacuum of -0.1MPa for 2 hours, and determine that the water content is ≤0.05wt%. Then release the vacuum and cool to 60°C for later use.

[0133] A2: Mix 10 parts by weight of ferrocene-modified polyether polyol S1 with 60 parts by weight of diphenyl diisocyanate MDI, and then mix with the intermediate material obtained in step A1 under a nitrogen atmosphere to carry out the reaction. The reaction temperature is 80℃ and the reaction time is 3h. After cooling to 40℃, filter and discharge to obtain prepolymer K1 with a viscosity of 1800mPa·s.

[0134] The polyurea resin composition M1 comprises: prepolymer K1, 35 parts by weight of amino-terminated polyether D2000, 30 parts by weight of chain extender diethyltoluene diamine, 20 parts by weight of ferrocene-modified amino-terminated polyether L1, 14 parts by weight of compound flame retardant C1 (a mixture of 60 parts by weight of triethyl phosphate TEP, 20 parts by weight of zinc borate and 20 parts by weight of char-forming agent pentaerythritol), 0.2 parts by weight of coupling agent Momentive A-187 silane coupling agent, 0.3 parts by weight of defoamer BYK A535 silicone defoamer, and 0.5 parts by weight of molecular sieve A3, wherein the isocyanate index of the polyurea resin composition M1 is 1.01.

[0135] Preparation of polyurea resin coating H1:

[0136] The polyurea resin was mixed and filtered with all components of composition M1 except prepolymer K1 for 1 hour. The filtered filtrate was then mixed with prepolymer K1, and the mixture was sprayed onto the substrate using a spraying device. The spraying environment was 15-40℃, the relative humidity was ≤80%, the spraying temperature was 65℃, the dynamic pressure was >13.8MPa, the curing temperature was 20℃, and the curing time was 7 days. The thickness of the polyurea resin coating H1 after curing was 2mm.

[0137] Example 2

[0138] Preparation of nickel-ceramic modified amino-terminated polyether L2:

[0139] 1,1'-dichlorocarbonyl nickel diacene was dissolved in 700 parts by weight of toluene, and then polyoxypropylene diamine D400 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polyoxypropylene diamine D400 and 1,1'-dichlorocarbonyl nickel diacene was 2.1:1. The pH of the mixture was adjusted to 7.8 using a 6.25 wt% sodium hydroxide solution, and the mixture was stirred at room temperature (20 °C) for 30 min to carry out the first reaction. The resulting intermediate material was then filtered, and the intermediate liquid phase was washed with chloroform and then dried to obtain nickel diacene-modified amino-terminated polyether L2 (weight average molecular weight of 1281).

[0140] Preparation of nickel-ceramic modified polyether polyol S2:

[0141] 1,1'-dichlorocarbonyl nickel diacene was dissolved in 100 parts by weight of toluene, and then polyethylene oxide glycol PEG600 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polyethylene oxide glycol PEG600 and 1,1'-dichlorocarbonyl nickel diacene was 2.1:1. The pH of the mixture was adjusted to 8 using 10 parts by weight of pyridine, and the mixture was stirred at 75°C for 4 hours to carry out the second reaction. The obtained intermediate material was then filtered, and the obtained intermediate liquid phase was concentrated. The concentrated material was extracted using dichloromethane as an extraction solvent, and then washed with water. The obtained organic layer was then dried and concentrated again to obtain nickel diacene-modified polyether polyol S2 (weight average molecular weight of 1473).

[0142] Preparation of prepolymer K2:

[0143] A1: Mix 20 parts by weight of polyether polyol Y1030 and 15 parts by weight of polycarbonate diol Desmophen C1100, heat to 115°C, dehydrate under vacuum of -0.1MPa for 2.5h, and determine that the water content is ≤0.05wt%. Then release the vacuum and cool to 50°C for later use.

[0144] A2: Mix 5 parts by weight of nickel-ceramic modified polyether polyol S2 with 60 parts by weight of isophorone diisocyanate, and then mix with the intermediate material obtained in step A1 under a nitrogen atmosphere to react. The reaction temperature is 85℃ and the reaction time is 2h. After cooling to 50℃, filter and discharge to obtain prepolymer K2 with a viscosity of 1650mPa·s.

[0145] The polyurea resin composition M2 comprises: prepolymer K2, 25 parts by weight of amino-terminated polyether T5000, 45 parts by weight of chain extender dimethyl thiotoluene diamine, 10 parts by weight of nickel-ceramic modified amino-terminated polyether L2, 19 parts by weight of compound flame retardant C2 (a mixture of 55 parts by weight of triethyl phosphate TEP, 20 parts by weight of zinc borate and 25 parts by weight of char-forming agent pentaerythritol), 0.2 parts by weight of coupling agent Momentive A-187 silane coupling agent, 0.3 parts by weight of defoamer BYK A535 silicone defoamer, and 0.5 parts by weight of molecular sieve A3, wherein the isocyanate index of the polyurea resin composition M2 is 1.03.

[0146] Preparation of polyurea resin coating H2:

[0147] The polyurea resin was mixed and filtered with all components of composition M2 except prepolymer K2 for 1 hour. The filtered filtrate was then mixed with prepolymer K2, and the mixture was sprayed onto the substrate using a spraying device. The spraying environment was 15-40℃, the relative humidity was ≤80%, the spraying temperature was 65℃, the dynamic pressure was >13.8MPa, the curing temperature was 20℃, and the curing time was 7 days. The thickness of the polyurea resin coating H2 after curing was 2mm.

[0148] Example 3

[0149] Preparation of cobalt-cerocenyl modified amino-terminated polyether L3:

[0150] 1,1'-dichlorocarbonyl cobaltene was dissolved in 700 parts by weight of toluene, and then polyoxypropylene diamine D400 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polyoxypropylene diamine D400 and 1,1'-dichlorocarbonyl cobaltene was 2.1:1. The pH of the mixture was adjusted to 7.8 using a 6.25 wt% sodium hydroxide solution, and the mixture was stirred at room temperature (20 °C) for 30 min to carry out the first reaction. The resulting intermediate material was then filtered, and the intermediate liquid phase was washed with chloroform and then dried to obtain cobaltene-modified amino-terminated polyether L3 (weight average molecular weight of 1282).

[0151] Preparation of cobalt-cerotropy-modified polyether polyol S3:

[0152] 1,1'-Dichlorocarbonyl cobaltene was dissolved in 100 parts by weight of toluene, and then polyethylene oxide glycol PPG600 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polyethylene oxide glycol PPG600 and 1,1'-dichlorocarbonyl cobaltene was 2.1:1. The pH of the mixture was adjusted to 8 using 10 parts by weight of pyridine, and the mixture was stirred at 75°C for 4 hours to carry out the second reaction. The obtained intermediate material was then filtered, and the obtained intermediate liquid phase was concentrated. The concentrated material was extracted using dichloromethane as an extraction solvent, and then washed with water. The obtained organic layer was then dried and concentrated again to obtain cobaltene-modified polyether polyol S3 (weight average molecular weight of 1472).

[0153] Preparation of prepolymer K3:

[0154] A1: Mix 15 parts by weight of polyether polyol 1000LM and 12 parts by weight of polycarbonate diol Desmophen C1200, heat to 105°C, dehydrate under vacuum of -0.1MPa for 4 hours, and determine that the water content is ≤0.05wt%. Then release the vacuum and cool to 50°C for later use.

[0155] A2: Mix 8 parts by weight of cobalt cyclohexylmethane diisocyanate with 65 parts by weight of cobalt cyclohexylmethane diisocyanate, and then mix with the intermediate material obtained in step A1 under a nitrogen atmosphere to react. The reaction temperature is 85°C and the reaction time is 3 hours. After cooling to 50°C, filter and discharge to obtain prepolymer K3 with a viscosity of 1900 mPa·s.

[0156] The polyurea resin composition M3 comprises: prepolymer K3, 60 parts by weight of amino-terminated polyether T403, 10 parts by weight of chain extender N,N′-bis-sec-pentylcyclohexanediamine, 15 parts by weight of cobalt-cerotropylated amino-terminated polyether L3, 14 parts by weight of compound flame retardant C3 (a mixture of 60 parts by weight of triethyl phosphate TEP, 25 parts by weight of zinc borate and 15 parts by weight of char-forming agent pentaerythritol), 0.2 parts by weight of coupling agent Momentive A-187 silane coupling agent, 0.3 parts by weight of defoamer BYK A535 silicone defoamer, and 0.5 parts by weight of molecular sieve A3, wherein the isocyanate index of the polyurea resin composition M3 is 1.05;

[0157] Preparation of polyurea resin coating H3:

[0158] The polyurea resin was mixed and filtered with all components of composition M3 except prepolymer K3 for 1 hour. The filtered filtrate was then mixed with prepolymer K3, and the mixture was sprayed onto the substrate using a spraying device. The spraying environment was 15-40℃, the relative humidity was ≤80%, the spraying temperature was 65℃, the dynamic pressure was >13.8MPa, the curing temperature was 20℃, and the curing time was 7 days. The thickness of the polyurea resin coating H3 after curing was 2mm.

[0159] Example 4

[0160] Preparation of ferrocene-modified amino-terminated polyether L4:

[0161] 1,1'-Dichlorocarbonylferrocene was dissolved in 700 parts by weight of toluene, and then polyoxypropylene diamine D2000 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polyoxypropylene diamine D2000 and 1,1'-dichlorocarbonylferrocene was 2.1:1. The pH of the mixture was adjusted to 7.8 using a 6.25 wt% sodium hydroxide solution, and the mixture was stirred at room temperature (20 °C) for 30 min to carry out the first reaction. The resulting intermediate material was then filtered, and the intermediate liquid phase was washed with chloroform and then dried to obtain ferrocene-modified amino-terminated polyether L4 (weight average molecular weight of 2878).

[0162] Preparation of ferrocene-modified polyether polyol S4:

[0163] 1,1'-Dichlorocarbonylferrocene was dissolved in 100 parts by weight of toluene, and then polytetrahydrofuran ether glycol PTMG650 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polytetrahydrofuran ether glycol PTMG650 and 1,1'-dichlorocarbonylferrocene was 2.1:1. The pH of the mixture was adjusted to 8 using 10 parts by weight of pyridine, and the mixture was stirred at 75°C for 4 hours to carry out the second reaction. The obtained intermediate material was then filtered, and the obtained intermediate liquid phase was concentrated. The concentrated material was extracted using dichloromethane as an extraction solvent, and then washed with water. The obtained organic layer was then dried and concentrated again to obtain ferrocene-modified polyether polyol S4 (weight average molecular weight of 1525).

[0164] Preparation of prepolymer K4:

[0165] A1: Mix 20 parts by weight of polyether polyol 1000LM and 10 parts by weight of polycarbonate diol Desmophen C1100, heat to 125°C, dehydrate under vacuum of -0.1MPa for 2 hours, and determine that the water content is ≤0.05wt%. Then release the vacuum and cool to 50°C for later use.

[0166] A2: Mix 5 parts by weight of ferrocene-modified polyether polyol S4 with 65 parts by weight of hexamethylene diisocyanate, and then mix with the intermediate material obtained in step A1 under a nitrogen atmosphere to react. The reaction temperature is 90℃ and the reaction time is 2h. After cooling to 50℃, filter and discharge to obtain prepolymer K4 with a viscosity of 1950mPa·s.

[0167] The polyurea resin composition M4 comprises: prepolymer K4, 60 parts by weight of amino-terminated polyether D400, 15 parts by weight of chain extender diethyltoluene diamine, 10 parts by weight of ferrocene-modified amino-terminated polyether L4, 14 parts by weight of compound flame retardant C4 (a mixture of 50 parts by weight of triethyl phosphate TEP, 25 parts by weight of zinc borate and 25 parts by weight of char-forming agent pentaerythritol), 0.2 parts by weight of coupling agent Momentive A-187 silane coupling agent, 0.3 parts by weight of defoamer BYK A535 silicone defoamer, and 0.5 parts by weight of molecular sieve A3, wherein the isocyanate index of the polyurea resin composition M4 is 1.04.

[0168] Preparation of polyurea resin coating H4:

[0169] The polyurea resin was mixed and filtered with all components of composition M4 except prepolymer K4 for 1 hour. The filtered filtrate was then mixed with prepolymer K4, and the mixture was sprayed onto the substrate using a spraying device. The spraying environment was 15-40℃, the relative humidity was ≤80%, the spraying temperature was 65℃, the dynamic pressure was >13.8MPa, the curing temperature was 20℃, and the curing time was 7 days. The thickness of the polyurea resin coating H4 obtained after curing was 2mm.

[0170] Example 5

[0171] Preparation of ferrocene-modified amino-terminated polyether L5:

[0172] 1,1'-Dichlorocarbonylferrocene was dissolved in 700 parts by weight of toluene, and then amino-terminated trimethylolpropane tripropylene glycol ether was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of amino-terminated trimethylolpropane tripropylene glycol ether to 1,1'-dichlorocarbonylferrocene was 2.1:1. The pH of the mixture was adjusted to 7.8 using 6.25 wt% sodium hydroxide solution, and the mixture was stirred at room temperature (20 °C) for 30 min to carry out the first reaction. The obtained intermediate material was then filtered, and the intermediate liquid phase was washed with chloroform and then dried to obtain ferrocene-modified amino-terminated polyether L5 (weight average molecular weight of 1281).

[0173] Preparation of ferrocene-modified polyether polyol S5:

[0174] 1,1'-Dichlorocarbonylferrocene was dissolved in 100 parts by weight of toluene, and then polypropylene glycol PPG600 was added under a nitrogen atmosphere to obtain a mixture, wherein the molar ratio of polypropylene glycol PPG600 and 1,1'-dichlorocarbonylferrocene was 2.1:1. The pH of the mixture was adjusted to 8 using 10 parts by weight of pyridine, and the mixture was stirred at 70°C for 4 hours to carry out the second reaction. The obtained intermediate material was then filtered, and the obtained intermediate liquid phase was concentrated. The concentrated material was extracted using dichloromethane as an extraction solvent, and then washed with water. The obtained organic layer was then dried and concentrated again to obtain ferrocene-modified polyether polyol S5 (weight average molecular weight of 1473).

[0175] Preparation of prepolymer K5:

[0176] A1: Mix 15 parts by weight of polyether polyol DL1000 and 10 parts by weight of polycarbonate diol Desmophen C1100, heat to 110°C, dehydrate under vacuum of -0.1MPa for 3 hours, and determine that the water content is ≤0.05wt%. Then release the vacuum and cool to 50°C for later use.

[0177] A2: Mix 10 parts by weight of ferrocene-modified polyether polyol S5 with 65 parts by weight of diphenyl diisocyanate MDI, and then mix with the intermediate material obtained in step A1 under a nitrogen atmosphere to react. The reaction temperature is 80℃ and the reaction time is 3h. After cooling to 50℃, filter and discharge to obtain prepolymer K5 with a viscosity of 1700mPa·s.

[0178] The polyurea resin composition M5 comprises: prepolymer K5, 20 parts by weight of amino-terminated polyether D2000, 55 parts by weight of chain extender 4,4′-bis-secylaminodiphenylmethane, 10 parts by weight of ferrocene-modified amino-terminated polyether L5, 14 parts by weight of compound flame retardant C5 (a mixture of 60 parts by weight of triethyl phosphate TEP, 20 parts by weight of zinc borate and 20 parts by weight of charring agent HF-T1020), 0.2 parts by weight of coupling agent Momentive A-187 silane coupling agent, 0.3 parts by weight of defoamer BYK A535 silicone defoamer, and 0.5 parts by weight of molecular sieve A3, wherein the isocyanate index of the polyurea resin composition M5 is 1.08.

[0179] Preparation of polyurea resin coating H5:

[0180] The polyurea resin was mixed with all components of composition M5 except prepolymer K5 for 1 hour and then filtered. The filtrate was then mixed with prepolymer K5, and the mixture was sprayed onto the substrate using a spraying device. The spraying environment was 15-40℃, the relative humidity was ≤80%, the spraying temperature was 65℃, the dynamic pressure was >13.8MPa, the curing temperature was 20℃, and the curing time was 7 days. The thickness of the polyurea resin coating H5 after curing was 2mm.

[0181] Example 6

[0182] The implementation was carried out in accordance with Example 1, except that the molar ratio of polyoxypropylene diamine D400 and 1,1'-dichlorocarbonyl ferrocene was 2.4:1.

[0183] Example 7

[0184] The implementation was carried out as described in the example, except that the molar ratio of polyoxypropylene diamine D400 and 1,1'-dichlorocarbonyl ferrocene was 2.8:1.

[0185] Example 8

[0186] The implementation was carried out in accordance with Example 1, except that the molar ratio of ethylene glycol PEG600 and 1,1'-dichlorocarbonyl ferrocene was 2.4:1.

[0187] Example 9

[0188] The implementation was carried out as described in the example, except that the molar ratio of ethylene glycol PEG600 and 1,1'-dichlorocarbonyl ferrocene was 2.8:1.

[0189] Comparative Example 1

[0190] The implementation was carried out in accordance with Example 1, except that 5 parts by weight of polycarbonate diol Tosoh981 and 5 parts by weight of diphenyl diisocyanate were used to replace 10 parts by weight of ferrocene-modified polyether polyol S1.

[0191] Comparative Example 2

[0192] The implementation was carried out in accordance with Example 1, except that 10 parts by weight of ferrocene-modified terminal amino-terminated polyether L1 were replaced with 5 parts by weight of terminal amino-terminated polyether D2000 and 5 parts by weight of compound flame retardant C1.

[0193] Comparative Example 3

[0194] The implementation was carried out in accordance with Example 1, except that 5 parts by weight of polycarbonate diol Tosoh981 and 5 parts by weight of diphenyl diisocyanate were used to replace 10 parts by weight of ferrocene-modified polyether polyol S1; and 10 parts by weight of ferrocene-modified ferrocene-modified ferrocene-modified polyether L1 were used to replace 10 parts by weight of amino-terminated polyether D2000.

[0195] Comparative Example 4

[0196] The implementation was carried out in accordance with Example 1, except that 14 parts by weight of the compound flame retardant C1 was replaced with 14 parts by weight of terminal amino polyether D2000.

[0197] Comparative Example 5

[0198] The implementation was carried out in accordance with Example 1, except that 14 parts by weight of compound flame retardant C6 (a mixture of 50 parts by weight of zinc borate and 50 parts by weight of pentaerythritol charring agent) was used instead of 14 parts by weight of compound flame retardant C1.

[0199] Comparative Example 6

[0200] The implementation was carried out in accordance with Example 1, except that 14 parts by weight of triethyl phosphate (TEP) were used to replace 14 parts by weight of the compound flame retardant C1.

[0201] Comparative Example 7

[0202] The implementation was carried out in accordance with Example 1, except that 5 parts by weight of polycarbonate diol Tosoh981 and 5 parts by weight of diphenyl diisocyanate were used to replace 10 parts by weight of ferrocene-modified polyether polyol S1; 10 parts by weight of ferrocene-modified ferrocene-modified polyether L1 were used to replace 10 parts by weight of amino-terminated polyether D2000; and 14 parts by weight of triethyl phosphate TEP were used to replace 14 parts by weight of the compounded flame retardant C1.

[0203] Comparative Example 8

[0204] Modified amino-terminated polyether L1 was prepared according to Example 1;

[0205] Ferrocene-modified polyether polyol S1 was prepared according to Example 1;

[0206] Prepolymer K1 was prepared according to Example 1;

[0207] The polyurea resin composition M6 comprises: prepolymer K1, 35 parts by weight of amino-terminated polyether D2000, 30 parts by weight of chain extender diethyltoluene diamine, 20 parts by weight of ferrocene-modified amino-terminated polyether L1, 14 parts by weight of compound flame retardant C1 (a mixture of 60 parts by weight of triethyl phosphate TEP, 20 parts by weight of zinc borate and 20 parts by weight of char-forming agent pentaerythritol), 0.2 parts by weight of coupling agent Momentive A-187 silane coupling agent, 0.3 parts by weight of defoamer BYK A535 silicone defoamer, and 0.5 parts by weight of molecular sieve A3, wherein the isocyanate index of the polyurea resin composition M6 is 1.2;

[0208] Preparation of polyurea resin coating H6:

[0209] The polyurea resin was mixed and filtered with all components of composition M6 except prepolymer K1 for 1 hour. The filtered filtrate was then mixed with prepolymer K1, and the mixture was sprayed onto the substrate using a spraying device. The spraying environment was 15-40℃, the relative humidity was ≤80%, the spraying temperature was 65℃, the dynamic pressure was >13.8MPa, the curing temperature was 20℃, and the curing time was 7 days. The thickness of the polyurea resin coating H1 obtained after curing was 2mm.

[0210] Test case

[0211] The samples prepared in the examples and comparative examples were subjected to performance tests, and the test indicators are as follows:

[0212] (1) The tensile properties of the samples were determined according to the test procedure specified in GB / T528-2009. The test results are shown in Table 1.

[0213] (2) The tear strength of the sample was determined according to the test procedure specified in GB / T529. The test results are shown in Table 1.

[0214] (3) The Shore hardness of the sample was determined according to the test procedure specified in GB / T 531.1-2008. The test results are shown in Table 1.

[0215] (4) Test the oxygen index of the sample according to the test procedure specified in GB / T 2406.1-2008 to determine the flame retardant performance;

[0216] (5) The gas explosion resistance of the sample was determined according to the test procedure specified in T / CIESC 0019-2021. The test results are shown in Table 1.

[0217] Table 1

[0218]

[0219]

[0220] As can be seen from the results in Table 1, the polyurea resin described in this invention has good mechanical properties, flame retardant properties and explosion-proof properties. The polyurea coating prepared using the polyurea resin described in this invention has a good application prospect in the field of explosion-proof materials.

[0221] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A metallocene-modified amino-terminated polyether, characterized in that, The metallocene-modified amino-terminated polyether is obtained by modifying the first amino-terminated polyether with metallocene. The metal in the metallocene-modified amino-terminated polyether is a transition metal, and the weight-average molecular weight of the first amino-terminated polyether is 400-2000.

2. The metallocene-modified amino-terminated polyether according to claim 1, characterized in that, The metal in the metallocerocene-modified amino-terminated polyether is selected from chromium, manganese, vanadium, iron, cobalt, or nickel.

3. The metallocene-modified amino-terminated polyether according to claim 1 or 2, characterized in that, The weight-average molecular weight of the metallocene-modified amino-terminated polyether is 500-3000.

4. A method for preparing the metallocene-modified amino-terminated polyether according to any one of claims 1-3, characterized in that, The method includes: In the presence of a first organic solvent, the first terminal amino polyether and 1,1'-dichlorocarbonyl dimetallocene are subjected to a first reaction.

5. The method according to claim 4, characterized in that, The first organic solvent is selected from one or more of toluene, xylene, N,N-dimethylformamide and dimethyl sulfoxide.

6. The method according to claim 4 or 5, characterized in that, The molar ratio of the first terminal amino polyether to the 1,1'-dichlorocarbonyl dimetallocene is 2-2.4:

1.

7. The method according to claim 6, characterized in that, The conditions for the first reaction include: a temperature of 10-40℃ and a time of 10-60 min.

8. A composition for use with polyurea resin, characterized in that, The polyurea resin composition comprises a prepolymer, a second-terminated amino polyether, a chain extender, a metallocene-modified amino polyether, and a compounded flame retardant. The isocyanate index of the polyurea resin composition is 1-1.

1. The prepolymer is obtained by polymerization of isocyanate, second polyether polyol, metallocene-modified polyether polyol and polycarbonate diol; The metallocene-modified polyether polyol is obtained by modifying the first polyether polyol with metallocene; the metal in the metallocene-modified polyether polyol is a transition metal, and the weight-average molecular weight of the first polyether polyol is 400-800. The metallocene-modified amino-terminated polyether is the metallocene-modified amino-terminated polyether according to any one of claims 1-3; The compound flame retardant comprises triethyl phosphate, zinc borate, and a charring agent.

9. The composition for polyurea resin according to claim 8, characterized in that, The viscosity of the prepolymer is 1500-3000 mPa·s.

10. The composition for polyurea resin according to claim 8 or 9, characterized in that, Based on the total weight of isocyanate, second polyether polyol, metallocene-modified polyether polyol and polycarbonate diol used to prepare the prepolymer, the content of isocyanate is 40-70 wt%, the content of second polyether polyol is 10-40 wt%, the content of metallocene-modified polyether polyol is 5-20 wt%, and the content of polycarbonate diol is 1-20 wt%.

11. The composition for polyurea resin according to any one of claims 8-10, characterized in that, The method for preparing the prepolymer includes the following steps: A1: Mix the second polyether polyol and polycarbonate diol and heat to 100℃-130℃. Dehydrate under vacuum and determine the water content to be ≤0.05wt%. Then release the vacuum for later use. A2: Mix the metallocene-modified polyether polyol with isocyanate, then mix it with the intermediate material obtained in step A1 under a protective atmosphere to react, and then perform solid-liquid separation to obtain the prepolymer.

12. The composition for polyurea resin according to claim 11, characterized in that, In step A2, the reaction conditions include a temperature of 75-90℃ and a time of 2-4 hours.

13. The composition for polyurea resin according to claim 12, characterized in that, The second polyether polyol is selected from one or more of polyether polyol DL1000, polyether polyol Y1030 and polyether polyol 1000LM; Preferably, the isocyanate is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, phenylmethylene diisocyanate and lysine diisocyanate.

14. The composition for polyurea resin according to any one of claims 8-13, characterized in that, The weight-average molecular weight of the metallocene-modified polyether polyol is 500-2000.

15. The composition for polyurea resin according to any one of claims 8-14, characterized in that, The metal in the metallocerocene-modified polyether polyol is selected from chromium, manganese, vanadium, iron, cobalt, or nickel.

16. The composition for polyurea resin according to claim 15, characterized in that, The preparation method of the metallocene-modified polyether polyol includes: In the presence of a second organic solvent, the first polyether polyol and 1,1'-dichlorocarbonyl dimetallocene undergo a second reaction.

17. The composition for polyurea resin according to claim 16, characterized in that, The second organic solvent is selected from one or more of toluene, xylene, N,N-dimethylformamide and dimethyl sulfoxide.

18. The composition for polyurea resin according to claim 16 or 17, characterized in that, The molar ratio of the first polyether polyol to the 1,1'-dichlorocarbonyl dimetallocene is 2-2.4:

1.

19. The composition for polyurea resin according to any one of claims 16-18, characterized in that, The conditions for the second reaction include a temperature of 60-100℃ and a time of 1-5 hours.

20. The composition for polyurea resin according to any one of claims 8-19, characterized in that, The polyurea resin composition further contains additives selected from one or more of antisettling agents, coupling agents, and molecular sieves.

21. The composition for polyurea resin according to any one of claims 8-20, characterized in that, Based on the total weight of the second-terminated amino polyether, chain extender, metallocene-modified terminal amino polyether, compound flame retardant, and optional additives, the content of the second-terminated amino polyether is 10-60 wt%, the content of the chain extender is 10-60 wt%, the content of the metallocene-modified terminal amino polyether is 5-30 wt%, the content of the compound flame retardant is 10-25 wt%, and the content of the additives is 0-1.5 wt%.

22. The composition for polyurea resin according to claim 21, characterized in that, The second amino-terminated polyether is selected from one or more of amino-terminated polyether D2000, amino-terminated polyether T5000, amino-terminated polyether D400 and amino-terminated polyether T403. Preferably, the chain extender is selected from one or more of diethyltoluenediamine, dimethylthiotoluenediamine, N,N′-dialkyldiamine, 1,4-bis-sec-butylaminobenzene, 4,4′-bis-sec-methylaminodiphenylmethane, and N,N′-bis-sec-pentylcyclohexanediamine.

23. The composition for polyurea resin according to claim 22, characterized in that, Based on the total weight of the compound flame retardant, the content of triethyl phosphate is 50-80 wt%, the content of zinc borate is 10-25 wt%, and the content of charring agent is 10-35 wt%.

24. The composition for polyurea resin according to claim 23, characterized in that, The charring agent is selected from one or more of pentaerythritol, dipentaerythritol, sorbitol, and Sanqin charring agent HF-T1020.

25. A method for preparing polyurea resin, characterized in that, The method includes mixing the components of the polyurea resin composition according to any one of claims 8-24.

26. The polyurea resin prepared by the method of claim 25.

27. A method for preparing a polyurea resin coating, characterized in that, The method includes: spraying the polyurea resin of claim 26 onto a substrate and then curing it.

28. The method according to claim 27, characterized in that, The environmental conditions for spraying include: an ambient temperature of 20-25℃ and a relative humidity of 45-75%. Preferably, the spraying conditions include: a temperature of ≥65℃ and a dynamic pressure of >13.8MPa.

29. The method according to claim 28, characterized in that, The curing conditions include: a temperature of 15-40℃ and a time of ≥7 days; Preferably, the thickness of the polyurea resin coating obtained after curing is 2-10 mm.

30. The use of the polyurea resin according to claim 26 in explosion-proof materials.

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