Composition for polyurea resin, polyurea resin as well as preparation method and application of polyurea resin

Abstract

The invention relates to the technical field of functional materials, and discloses a composition for polyurea resin, the polyurea resin and a preparation method and application of the polyurea resin. The composition for the polyurea resin comprises a prepolymer, a polyaspartic acid ester chain extender, an aromatic steric hindrance chain extender, a cross-linking agent and optional auxiliaries, wherein the prepolymer is obtained by carrying out polymerization reaction on polymethylene polyphenyl isocyanate and an end-capping reagent. The polyurea resin prepared from the composition for the polyurea resin has good tensile strength and tearing strength, meets the performance of an anti-explosion material, does not contain volatile organic solvents, is environment-friendly and does not cause harm to constructors.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional materials, in particular to a polyurea resin composition, a polyurea resin and a preparation method and application thereof. BACKGROUND

[0002] Polyurea elastomer is a new type of material developed in the 1990s, which is obtained by reacting a semi-prepolymer (prepolymer) of hydroxyl-terminated polyether / polyester / amino polyether with isocyanate, and then reacting with a resin component composed of amino-terminated polyether and amino-terminated chain extender and other additives. Currently, the commercially available polyurea products mainly include sprayable two-component polyurea, two-component slow-curing polyaspartic acid polyurea and one-component drawdown polyurea.

[0003] Sprayable polyurea elastomer material has been widely used in waterproofing, corrosion protection and protection fields due to its fast film formation and curing, high strength and quick construction. In recent years, a large number of tests have confirmed that spraying high-strength polyurea elastomer on building walls and other components can significantly improve the blast resistance of buildings. In addition to absorbing blast impact energy, the polyurea coating can also encapsulate the fragments generated by the explosion, thereby maximizing the protection of the lives and safety of people inside the building. By spraying polyurea blast-resistant coating on buildings, equipment and facilities, the protection capability can be improved, and the internal personnel can be protected from blast impact damage. However, in actual application, sprayable polyurea is only suitable for large-area construction, and most existing buildings such as device control rooms and equipment cabinets have small internal spaces and are in service, which do not have the conditions to use sprayable polyurea technology for blast-resistant modification. Moreover, many petrochemical enterprises have 24-hour personnel in the existing buildings, in order to improve the adhesion strength, the current epoxy primer generally contains a large amount of organic solvent, which seriously damages the health of the operating personnel and construction personnel in the building. In addition, sprayable polyurea must be constructed using expensive professional spraying equipment, and the construction personnel also have high professional requirements, which to some extent limits the popularization and application of sprayable polyurea technology.

[0004] The single-component polyurea / polyurethane material is cured by using a latent curing agent to absorb moisture in the air to release amino groups and isocyanate to react, although the reaction speed is slowed down, but the disadvantage is that the mechanical properties are generally low and cannot be used in the anti-blast field, in addition, more than 10% of organic solvents are added for convenient construction, which cannot be used for anti-blast modification of existing buildings; the polyurea resin composition disclosed in patent application numbers CN201010525021.7 and CN201110054157.9 uses aromatic isocyanate and aromatic hindered amine as raw materials, the mechanical properties are greatly improved compared with traditional polyaspartic acid polyurea, but still cannot meet the anti-blast requirements; the anti-blast polyurea disclosed in patent application number CN201910567817.X belongs to a rigid material, and the elongation at break does not meet the requirements of anti-blast materials. SUMMARY

[0005] The purpose of the present application is to overcome the problems of poor mechanical properties of the existing polyurea resin, unsuitable for anti-blast modification of in-service buildings with narrow space, and unsuitable for facade construction, and to provide a polyurea resin composition, the polyurea resin prepared from the polyurea resin composition has excellent tensile strength and tear strength, high pull adhesion strength with the substrate, and does not contain volatile organic solvents.

[0006] In order to achieve the above-mentioned purpose, one aspect of the present application provides a polyurea resin composition, the polyurea resin composition comprises a prepolymer, a polyaspartic acid chain extender, an aromatic hindered chain extender, a crosslinking agent and an optional auxiliary agent.

[0007] The prepolymer is obtained by polymerization reaction of polymethylene polyphenyl isocyanate and a blocking agent.

[0008] Preferably, the total weight of the polyaspartic acid chain extender, the aromatic hindered chain extender, the crosslinking agent and the optional auxiliary agent and the weight of the prepolymer are in a ratio of 1:2-3.

[0009] Preferably, the blocking agent is selected from one or more of benzyl alcohol, phenoxyethanol and active diluent blocked linear monohydric alcohol.

[0010] Preferably, the weight average molecular weight of the active diluent blocked linear monohydric alcohol is 100-3000.

[0011] Preferably, the linear monohydric alcohol is selected from one or more of linear polypropylene oxide ether end group monohydric alcohol, linear polytetrahydrofuran ether end group monohydric alcohol, linear polycaprolactone end group monohydric alcohol and linear polycarbonate end group monohydric alcohol.

[0012] Preferably, the weight ratio of the polymethylene polyphenyl isocyanate and the blocking agent is 1:0.25-1.5.

[0013] Preferably, the prepolymer has a viscosity of 300-1000 mPa-S.

[0014] Preferably, the polymethylene polyphenyl isocyanate has a functionality of 2.5-3, a viscosity of 150-700 mPa-S, and an NCO value of 30-32.

[0015] Preferably, the polymethylene polyphenyl isocyanate is selected from PM-200, PM-300, or PM-400.

[0016] Preferably, the polyaspartic ester chain extender is present in an amount of 30-89 wt%, the aromatic hindered chain extender is present in an amount of 10-40 wt%, the crosslinking agent is present in an amount of 1-10 wt%, and the adjuvant is present in an amount of 0-9.5 wt%, based on the total weight of the polyaspartic ester chain extender, the aromatic hindered chain extender, the crosslinking agent, and the optional adjuvant.

[0017] Preferably, the adjuvant is selected from one or more of an adhesion promoter, a wetting dispersant, an antifoaming agent, and a water absorbent.

[0018] The second aspect of the present application provides a method for preparing a polyurea resin, the method comprising mixing the components of the polyurea resin composition described above.

[0019] Preferably, the method for preparing the prepolymer comprises polymerizing the polymethylene polyphenyl isocyanate and the capping agent, and then cooling and filtering the product.

[0020] Preferably, the polymerization conditions comprise a vacuum degree of -0.1 to 0.07 MPa, a temperature of 80-85°C, and a time of 2-4 h.

[0021] Preferably, the capping agent is selected from one or more of benzyl alcohol, phenoxyethanol, and an active diluent-capped linear monohydric alcohol.

[0022] The method for preparing the active diluent-capped linear monohydric alcohol comprises reacting the active diluent and the dihydric alcohol, and then cooling.

[0023] Preferably, the reaction conditions comprise a vacuum degree of -0.1 to 0.07 MPa, a temperature of 100-130°C, and a time of 2-4 h.

[0024] Preferably, the molar ratio of the active diluent to the dihydric alcohol is 1:2-4.

[0025] Preferably, the dihydric alcohol is selected from a linear polypropylene oxide ether dihydric alcohol, a linear polytetrahydrofuran ether dihydric alcohol, a linear polycaprolactone dihydric alcohol, or a linear polycarbonate dihydric alcohol.

[0026] Preferably, the weight average molecular weight of the dihydric alcohol is 100-3000.

[0027] The third aspect of the present application provides a polyurea resin prepared by the above method.

[0028] The fourth aspect of the present application provides an application of the above polyurea resin in an anti-blast material.

[0029] Compared with the prior art, the technical solution of the present application has the following advantages:

[0030] (1) The polyurea resin described in the present application has good mechanical properties, especially tensile strength and tear strength, which meet the performance of anti-blast materials, which is mainly due to the fact that the polyurea resin contains a large number of urea bonds and hydrogen bonds;

[0031] (2) The polyurea resin described in the present application does not contain volatile organic solvents, is environmentally friendly, and will not harm the construction personnel;

[0032] (3) The polyurea resin described in the present application has a slow curing speed, can be manually brushed, and has flexible construction conditions, which solves the problem that professional spraying polyurea equipment cannot be used in narrow spaces;

[0033] (4) The polyurea resin described in the present application has high adhesion strength with the substrate, which is mainly due to the fact that its curing speed is slow, and it can fully infiltrate the substrate. DETAILED DESCRIPTION

[0034] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0035] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and the values are approximate values and should be understood to include values approximately near these ranges and values within these ranges. For ranges of values, the endpoints of the ranges are combined with the individual points to form new ranges within the scope of the present application.

[0036] One aspect of the present application provides a polyurea resin composition, which comprises a prepolymer, a polyaspartic acid ester chain extender, an aromatic steric chain extender, a crosslinking agent, and an optional auxiliary agent.

[0037] The prepolymer is obtained by polymerization of polymethylene polyphenyl isocyanate and a blocking agent.

[0038] In the present application, the polyurea resin composition is obtained by a prepolymerization reaction of polymethylene polyphenyl isocyanate and a blocking agent, and the blocking agent added can reduce the curing speed of the polyurea resin composition during the curing process, making it suitable for manual brushing and flexible construction conditions, solving the problem that professional polyurea spraying equipment cannot be used in narrow spaces, and also providing good substrate infiltration and enhancing the pull strength and adhesion strength of the substrate; and the polyurea resin formed after the curing of the polyurea resin composition contains a large number of urea bonds and hydrogen bonds, has good tensile strength and tear strength, and the crosslinking agent can further improve the mechanical properties of the polyurea resin, so as to meet the requirements of the blast-resistant material; the polyurea resin composition does not contain volatile solvents, is environmentally friendly and will not harm the construction personnel.

[0039] In a preferred embodiment, in order to optimize the mechanical properties and curing rate of the polyurea resin after the curing of the polyurea resin composition, the total weight of the polyaspartic acid ester chain extender, the aromatic steric hindrance chain extender, the crosslinking agent and the optional auxiliary agent and the weight of the prepolymer are in a ratio of 1:2-3; specifically, it can be 1:2, 1:2.5 or 1:3.

[0040] In a more preferred embodiment, the viscosity of the prepolymer is 300-3000 mPa·S; specifically, the viscosity of the prepolymer can be 300 mPa·S, 600 mPa·S, 800 mPa·S, 1000 mPa·S, 1500 mPa·S, 2000 mPa·S, 2500 mPa·S or 3000 mPa·S.

[0041] In a preferred embodiment, in order to further control the chain length of the prepolymer, the weight ratio of the polymethylene polyphenyl isocyanate and the blocking agent is 1:0.25-1.5; specifically, the weight ratio of the polymethylene polyphenyl isocyanate and the blocking agent can be 1:0.25, 1:0.5, 1:0.75, 1:1, 1:1.25 or 1:1.5.

[0042] In a preferred embodiment, the functionality of the polymethylene polyphenyl isocyanate is 2.5-3, the viscosity is 150-700 mPa·S, and the NCO value is 30-32.

[0043] In the present application, the "NCO value" refers to the "mass of isocyanate (-NCO) groups contained in 100 g of sample".

[0044] In a preferred embodiment, the polymethylene polyphenyl isocyanate is selected from PM-200, PM-300 or PM-400.

[0045] In a preferred embodiment, the blocking agent is selected from one or two or more of benzyl alcohol, phenoxyethanol and active diluent blocked linear monohydric alcohol.

[0046] In the present application, there is no special requirement for the active release agent, and the commonly used in the art can be used, for example, it can be ethylene carbonate and / or propylene carbonate.

[0047] In the preferred embodiment, the weight average molecular weight of the active diluent-terminated linear monohydric alcohol is 100-3000.

[0048] In the preferred embodiment, the linear monohydric alcohol is selected from one or more of linear polyoxypropylene ether end group monohydric alcohol, linear polytetrahydrofuran ether end group monohydric alcohol, linear polycaprolactone end group monohydric alcohol and linear polycarbonate end group monohydric alcohol.

[0049] In the preferred embodiment, in order to further optimize the curing rate of the polyurea resin composition and the mechanical properties of the polyurea resin after curing, the content of the polyaspartic ester chain extender is 30-89wt%, the content of the aromatic steric chain extender is 10-40wt%, the content of the crosslinking agent is 1-10wt%, and the content of the auxiliary agent is 0-9.5wt%, based on the total weight of the polyaspartic ester chain extender, the aromatic steric chain extender, the crosslinking agent and the optional auxiliary agent.

[0050] In the preferred embodiment, the polyaspartic ester chain extender is a mixture of polyaspartic ester chain extender Desmophen NH XP-7068 and polyaspartic ester chain extender Desmophen NH 1420, and the weight ratio of the amount of use of the polyaspartic ester chain extender Desmophen NH XP-7068 and the polyaspartic ester chain extender Desmophen NH 1420 is 1:0.5-6; specifically, it can be 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5 or 1:6.

[0051] In the present application, there is no special requirement for the crosslinking agent, and the commonly used in the art can be used, for example, it can be tetra(2-hydroxypropyl)ethylenediamine.

[0052] In the preferred embodiment, the auxiliary agent is selected from one or more of adhesion promoter, wet dispersant, defoaming agent and water absorbing agent.

[0053] In the present application, there is no special requirement for the adhesion promoter, wet dispersant, defoaming agent and water absorbing agent, and the commonly used in the art can be used, for example, the adhesion promoter can be adhesion promoter AKN-6000; the wet dispersant can be wet dispersant BYK-W980; the defoaming agent can be defoaming agent A-535; and the water absorbing agent can be water absorbing agent A3.

[0054] The second aspect of the present application provides a method for preparing a polyurea resin, the method comprising mixing the components of the polyurea resin composition described above.

[0055] In the present application, there is no special requirement for the mixing method, and the mixing method commonly used in the art can be used, for example, stirring.

[0056] In a preferred embodiment, in order to control the chain length of the prepolymer, the method for preparing the prepolymer comprises polymerizing the polymethylene polyphenyl isocyanate and the blocking agent, and then cooling and filtering the product.

[0057] In a preferred embodiment, the conditions of the polymerization reaction comprise a vacuum degree of -0.1 to 0.07 MPa, a temperature of 80 to 85°C, and a time of 2 to 4 h; specifically, the vacuum degree can be -0.1 MPa, -0.05 MPa, 0 MPa, 0.05 MPa, or 0.07 MPa; the temperature can be 80°C, 81°C, 82°C, 83°C, 84°C, or 85°C; and the time can be 2 h, 2.5 h, 3 h, 3.5 h, or 4 h.

[0058] In a specific embodiment, the method for preparing the prepolymer comprises adding the blocking agent into a reaction kettle, then adding the polymethylene polyphenyl isocyanate under stirring, heating to 80 to 85°C for 2 to 4 h, then cooling to room temperature (10 to 30°C) and filtering the product.

[0059] In a preferred embodiment, the blocking agent is selected from one or two or more of benzyl alcohol, phenoxyethanol, and active diluent-terminated linear monohydric alcohol; wherein the method for preparing the active diluent-terminated linear monohydric alcohol comprises reacting the active diluent and the dihydric alcohol, and then cooling.

[0060] In a preferred embodiment, the conditions of the reaction comprise a vacuum degree of -0.1 to 0.07 MPa, a temperature of 100 to 130°C, and a time of 2 to 4 h; specifically, the vacuum degree can be -0.1 MPa, -0.05 MPa, 0 MPa, 0.05 MPa, or 0.07 MPa; the temperature can be 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, or 130°C; and the time can be 2 h, 2.5 h, 3 h, 3.5 h, or 4 h.

[0061] In a specific embodiment, the method for preparing the active diluent-terminated linear monohydric alcohol comprises adding the dihydric alcohol into a reaction kettle and heating, then adding the active diluent, heating to 100 to 130°C for 2 to 4 h, maintaining the vacuum degree at -0.1 to 0.07 MPa, releasing the moisture in the water trap every certain period of time until the moisture content is less than 0.05 wt%, and then cooling to room temperature (10 to 30°C).

[0062] In a preferred embodiment, the molar ratio of the active diluent to the dihydric alcohol is 1:2-4; specifically, the molar ratio of the active diluent to the dihydric alcohol can be 1:2, 1:3 or 1:4.

[0063] In a preferred embodiment, the dihydric alcohol is selected from linear polyoxypropylene ether dihydric alcohol, linear polytetrahydrofuran ether dihydric alcohol, linear polycaprolactone dihydric alcohol or linear polycarbonate dihydric alcohol.

[0064] In a preferred embodiment, the weight average molecular weight of the dihydric alcohol is 100-3000.

[0065] The third aspect of the present application provides a polyurea resin prepared by the above method.

[0066] In the present application, the polyurea resin has good tensile strength, tear strength and moderate curing speed, making it suitable for manual brushing and flexible construction conditions, solving the problem that professional spraying polyurea equipment cannot be used in narrow space, and also providing good substrate infiltration, enhancing the pull strength and adhesion strength with the substrate, meeting the requirements of blast-resistant materials, and the polyurea resin does not contain volatile solvents, is environmentally friendly and does not harm the construction personnel.

[0067] The fourth aspect of the present application provides the use of the above polyurea resin in blast-resistant materials.

[0068] The polyurea resin prepared by the present application can effectively coat the wall fragments generated by the masonry wall under the action of the explosion shock wave, preventing the wall fragments from causing secondary damage to personnel.

[0069] The following examples further illustrate the polyurea resin composition and polyurea resin of the present application, as well as the preparation method and application thereof. The examples are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following examples.

[0070] The experimental methods in the following examples and comparative examples are the conventional methods in the art, unless otherwise specified. The experimental materials used in the following examples and comparative examples are commercially available, unless otherwise specified. Specifically, the polymeric methylene polyphenyl isocyanate (PM-200, MDI content < 50%), the polymeric methylene polyphenyl isocyanate (PM-300, MDI content < 50%) and the polymeric methylene polyphenyl isocyanate (PM-400, MDI content < 50%) are all purchased from Wanhua Chemical Co., Ltd.; MDI 50 is purchased from Wanhua Chemical Co., Ltd.; the linear polyoxypropylene ether diol DL1000 is purchased from Bluestar Eastda Co., Ltd.; the linear polytetramethylene ether glycol PTMG1000 is purchased from Mitsubishi Chemical Corporation; the linear polycaprolactone diol PCL N210 is purchased from Daicel Corporation; the linear polycarbonate diol PCDL980 is purchased from DKS Co., Ltd.; the propylene carbonate and the ethylene carbonate are purchased from Yantai Yuandong Fine Chemical Co., Ltd.; the polyaspartic ester chain extender Desmophen NH XP-7068 is purchased from Covestro Co., Ltd.; the polyaspartic ester chain extender Desmophen NH 1420 is purchased from Covestro Co., Ltd.; the aromatic steric hindrance chain extender wanalink 6200 is purchased from Wanhua Chemical Co., Ltd.; the tetra(2-hydroxypropyl) ethylenediamine is purchased from Jiaxing Baolailai Resin Chemical Co., Ltd.; the adhesion promoter AKN6000 is purchased from Foshan Qianyou Chemical Co., Ltd.; the wetting and dispersing agent BYK W980 is purchased from BYK-Chemie GmbH; the defoaming agent A-535 is purchased from BYK-Chemie GmbH; and the water absorbent A3 is purchased from Gris Chemical Co., Ltd.

[0071] Example 1

[0072] The raw materials for preparing the polyurea resin S1 contain 70 parts by weight of PM-200, 30 parts by weight of benzyl alcohol, 20 parts by weight of the polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of the polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of the aromatic steric hindrance chain extender WANALINK 6200, 8 parts by weight of the crosslinking agent tetra(2-hydroxypropyl) ethylenediamine, 0.5 parts by weight of the adhesion promoter AKN6000, 0.5 parts by weight of the wetting and dispersing agent BYK W980, 0.5 parts by weight of the defoaming agent A-535 and 5.5 parts by weight of the water absorbent A3, i.e. the weight ratio of the polymeric methylene polyphenyl isocyanate (PM-200) and the blocking agent (benzyl alcohol) is 1:0.43, and the weight ratio of the polyaspartic ester chain extender Desmophen NH XP-7068 and the polyaspartic ester chain extender Desmophen NH 1420 is 1:2.

[0073] Preparation of prepolymer M1: 30 parts by weight of benzyl alcohol was added to a reaction kettle, heated to 100°C, vacuumized for 2h under stirring, cooled to room temperature 20°C, then 70 parts by weight of PM-200 was slowly added, heated to 85°C for 3h, cooled to room temperature 20°C, then filtered out the material, to obtain prepolymer M1 (viscosity 850 mPa·S at 25°C);

[0074] Preparation of polyurea resin S1:

[0075] 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts by weight of water absorbent A3 were stirred and mixed, the mixing rate was 800 rpm, the mixing time was 30 min, then the prepolymer M1 was added, wherein the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic steric chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of prepolymer M1 were 1:2, to obtain polyurea resin S1.

[0076] Example 2

[0077] The raw materials for preparing polyurea resin S2 contained: 60 parts by weight of PM-200, 30 parts by weight of benzyl alcohol, 10 parts by weight of phenoxyethanol, 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts by weight of water absorbent A3, i.e. the weight ratio of polymethylene polyphenyl isocyanate (PM-200) and capping agent (benzyl alcohol and phenoxyethanol) was 1:0.67, and the weight ratio of polyaspartic ester chain extender Desmophen NH XP-7068 and polyaspartic ester chain extender Desmophen NH 1420 was 1:2.

[0078] Preparation of prepolymer M2: 30 parts by weight of benzyl alcohol and 10 parts by weight of phenoxyethanol were added to a reaction kettle, heated to 100°C, vacuumed for 2h under stirring, cooled to room temperature 20°C, then 60 parts by weight of PM-200 was slowly added, heated to 85°C for 3h, cooled to room temperature 20°C, then filtered out the material, and prepolymer M2 (viscosity 960 mPa·S at 25°C) was obtained;

[0079] Preparation of polyurea resin S2:

[0080] 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic hindered chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts of water absorbent A3 were stirred and mixed, the mixing rate was 800 rpm, the mixing time was 30 min, then the prepolymer M2 was added, wherein the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic hindered chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of prepolymer M2 was 1:2, and polyurea resin S2 was obtained.

[0081] Example 3

[0082] The raw materials for preparing the polyurea resin S3 include 60 parts by weight of PM-300, 30 parts by weight of benzyl alcohol, 10 parts by weight of phenoxyethanol, 20 parts by weight of the polyaspartic acid ester chain extender Desmophen NH XP-7068, 40 parts by weight of the polyaspartic acid ester chain extender Desmophen NH 1420, 25 parts by weight of the aromatic steric hindrance chain extender WANALINK 6200, 8 parts by weight of the crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of the adhesion promoter AKN6000, 0.5 parts by weight of the wetting dispersant BYK W980, 0.5 parts by weight of the defoaming agent A-535, and 5.5 parts by weight of the water absorbent A3, i.e., the weight ratio of the polymethylene polyphenyl isocyanate (PM-300) and the capping agent (benzyl alcohol and phenoxyethanol) is 1:0.67, and the weight ratio of the polyaspartic acid ester chain extender Desmophen NH XP-7068 and the polyaspartic acid ester chain extender Desmophen NH 1420 is 1:2.

[0083] Preparation of the prepolymer M3: 30 parts by weight of benzyl alcohol and 10 parts by weight of phenoxyethanol were added to a reaction kettle, heated to 100°C, and vacuumized for 2 hours under stirring, and then cooled to room temperature 20°C, and then 60 parts by weight of PM-300 was slowly added, heated to 85°C, and reacted for 3 hours, and then cooled to room temperature 20°C, and then the product was filtered to obtain the prepolymer M3 (25°C viscosity 980 mPa·S);

[0084] Preparation of the polyurea resin S3:

[0085] 20 parts by weight of the polyaspartic acid ester chain extender Desmophen NH XP-7068, 40 parts by weight of the polyaspartic acid ester chain extender Desmophen NH 1420, 25 parts by weight of the aromatic steric hindrance chain extender WANALINK 6200, 8 parts by weight of the crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of the adhesion promoter AKN6000, 0.5 parts by weight of the wetting dispersant BYK W980, 0.5 parts by weight of the defoaming agent A-535, and 5.5 parts by weight of the water absorbent A3 were stirred and mixed at a rate of 800 rpm for 30 minutes, and then the prepolymer M3 was added after uniform mixing, wherein the total weight of the polyaspartic acid ester chain extender Desmophen NH XP-7068, the polyaspartic acid ester chain extender Desmophen NH 1420, the aromatic steric hindrance chain extender WANALINK 6200, the crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, the adhesion promoter AKN6000, the wetting dispersant BYK W980, the defoaming agent A-535, and the water absorbent A3 and the weight of the prepolymer M3 is 1:2, to obtain the polyurea resin S3.

[0086] Example 4

[0087] The raw materials for preparing the polyurea resin S4 include 60 parts by weight of PM-400, 30 parts by weight of benzyl alcohol, 10 parts by weight of phenoxyethanol, 10 parts by weight of the polyaspartic acid ester chain extender Desmophen NH XP-7068, 40 parts by weight of the polyaspartic acid ester chain extender Desmophen NH 1420, 32 parts by weight of the aromatic steric chain extender WANALINK 6200, 10 parts by weight of the crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of the adhesion promoter AKN6000, 0.5 parts by weight of the wetting dispersant BYK W980, 0.5 parts by weight of the defoaming agent A-535, and 6.5 parts by weight of the water absorption agent A3, that is, the weight ratio of the polymethylene polyphenyl isocyanate (PM-400) and the blocking agent (benzyl alcohol and phenoxyethanol) is 1:0.67, and the weight ratio of the polyaspartic acid ester chain extender Desmophen NH XP-7068 and the polyaspartic acid ester chain extender Desmophen NH 1420 is 1:4;

[0088] Preparation of the prepolymer M4: 30 parts by weight of benzyl alcohol and 10 parts by weight of phenoxyethanol were added to a reaction kettle, heated to 100°C, and vacuumized for 2 hours under stirring, and then cooled to room temperature 20°C, and then 60 parts by weight of PM-400 was slowly added, heated to 85°C, and reacted for 3 hours, and then cooled to room temperature 20°C, and then the product was filtered to obtain the prepolymer M4 (25°C viscosity 1000 mPa·S);

[0089] Preparation of the polyurea resin S4:

[0090] 10 parts by weight of the polyaspartic acid ester chain extender Desmophen NH XP-7068, 40 parts by weight of the polyaspartic acid ester chain extender Desmophen NH 1420, 32 parts by weight of the aromatic steric chain extender WANALINK 6200, 10 parts by weight of the crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of the adhesion promoter AKN6000, 0.5 parts by weight of the wetting dispersant BYK W980, 0.5 parts by weight of the defoaming agent A-535, and 6.5 parts by weight of the water absorption agent A3 were stirred and mixed at a rate of 800 rpm for 30 minutes, and then the prepolymer M4 was added after uniform mixing, wherein the total weight of the polyaspartic acid ester chain extender Desmophen NH XP-7068, the polyaspartic acid ester chain extender Desmophen NH 1420, the aromatic steric chain extender WANALINK 6200, the crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, the adhesion promoter AKN6000, the wetting dispersant BYK W980, the defoaming agent A-535, and the water absorption agent A3 and the weight of the prepolymer M4 were in a ratio of 1:2, and the polyurea resin S4 was obtained.

[0091] Example 5

[0092] The raw materials for preparing the polyurea resin S5 contain: 60 parts by weight of PM-300, 40 parts by weight of propylene carbonate-terminated linear polyoxypropylene ether monol, 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric hindrance chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535, and 5.5 parts of water absorption agent A3, i.e. the weight ratio of the polyisocyanate (PM-300) and the blocking agent (propylene carbonate-terminated linear polyoxypropylene ether monol) is 1:0.67, and the weight ratio of the polyaspartic ester chain extender Desmophen NH XP-7068 and the polyaspartic ester chain extender Desmophen NH 1420 is 1:2;

[0093] Preparation of propylene carbonate-terminated linear polyoxypropylene ether monol:

[0094] A linear polyoxypropylene ether diol DL1000 with a weight average molecular weight of 1000 was added to a reaction kettle, heated to 60°C and kept, then propylene carbonate was added, heated to 120°C and reacted for 5h, the molar ratio of propylene carbonate to linear polyoxypropylene ether diol DL1000 was 1:2, and the vacuum degree was kept at 0.05 MPa during the reaction. The water evaporated in the water trap was discharged every 1h until the water content was less than 0.05wt%, and then cooled to room temperature (20°C) for standby;

[0095] Preparation of prepolymer M5: 40 parts by weight of propylene carbonate-terminated linear polyoxypropylene ether monol was added to a reaction kettle, heated to 100°C, and vacuumed for 2h under stirring. After cooling to room temperature 20°C, 60 parts by weight of PM-300 was slowly added, heated to 85°C and reacted for 3h. After cooling to room temperature 20°C, the product was filtered out to obtain the prepolymer M5 (viscosity 1050 mPa·S at 25°C);

[0096] Preparation of polyurea resin S5:

[0097] The 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts by weight of water absorbent A3 are stirred and mixed, the mixing rate is 800 rpm, the time is 30 min, after uniform mixing, the prepolymer M5 is added, wherein the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic steric chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of the prepolymer M5 are in a ratio of 1:2, to obtain a polyurea resin S5.

[0098] Example 6

[0099] The raw materials for preparing the polyurea resin S6 contain: 60 parts by weight of PM-300, 40 parts by weight of propylene carbonate-terminated linear polytetrahydrofuran ether terminal monohydric alcohol, 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts by weight of water absorbent A3, that is, the weight ratio of polymethylene polyphenyl isocyanate (PM-300) and capping agent (propylene carbonate-terminated linear polytetrahydrofuran ether terminal monohydric alcohol) is 1:0.67, and the weight ratio of polyaspartic ester chain extender Desmophen NH XP-7068 and polyaspartic ester chain extender Desmophen NH 1420 is 1:2.

[0100] Preparation of propylene carbonate-terminated linear polytetrahydrofuran ether terminal monohydric alcohol:

[0101] A reaction kettle was charged with linear polytetrahydrofuran ether end group dihydric alcohol PTMG1000 with a weight average molecular weight of 1000, heated to 60°C, then propylene carbonate was added, heated to 120°C and reacted for 5h, the molar ratio of propylene carbonate to linear polytetrahydrofuran ether end group dihydric alcohol PTMG1000 was 1:2, the vacuum degree was maintained at 0.05 MPa during the reaction, the water vapor in the water trap was discharged every 1h until the water content was less than 0.05wt%, and then cooled to room temperature (20°C) for standby;

[0102] Preparation of prepolymer M6: 40 parts by weight of propylene carbonate-terminated linear polytetrahydrofuran ether end group monohydric alcohol was added to a reaction kettle, heated to 100°C, and vacuumed for 2h under stirring, then slowly added 60 parts by weight of PM-300 after cooling to room temperature 20°C, heated to 85°C and reacted for 3h, then filtered the material after cooling to room temperature 20°C, to obtain prepolymer M6 (viscosity 1080 mPa·S at 25°C);

[0103] Preparation of polyurea resin S6:

[0104] 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric hindrance chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl) ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts of water absorbent A3 were stirred and mixed, the mixing rate was 800 rpm, the mixing time was 30 min, then the prepolymer M6 was added after uniform mixing, wherein the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic steric hindrance chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl) ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of prepolymer M6 was 1:2, to obtain polyurea resin S6.

[0105] Example 7

[0106] The raw materials for preparing the polyurea resin S7 contain: 50 parts by weight of PM-300, 50 parts by weight of propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol, 15 parts by weight of the polyaspartic acid ester chain extender Desmophen NH XP-7068, 45 parts by weight of the polyaspartic acid ester chain extender Desmophen NH 1420, 21 parts by weight of the aromatic steric hindrance chain extender WANALINK 6200, 10 parts by weight of the crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of the adhesion promoter AKN6000, 0.5 parts by weight of the wetting dispersant BYK W980, 0.5 parts by weight of the defoaming agent A-535, and 7.5 parts of the water absorption agent A3, that is, the weight ratio of the polymeric methylene polyphenyl isocyanate (PM-300) and the blocking agent (propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol) is 1:1, and the weight ratio of the polyaspartic acid ester chain extender Desmophen NH XP-7068 and the polyaspartic acid ester chain extender Desmophen NH 1420 is 1:3;

[0107] The propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol is prepared as follows:

[0108] The linear polytetramethylene ether end group dihydric alcohol PTMG1000 with a weight average molecular weight of 1000 is added to a reaction kettle, heated to 60°C, and then propylene carbonate is added. The mixture is heated to 120°C and reacted for 5 hours. The molar ratio of propylene carbonate to the linear polytetramethylene ether end group dihydric alcohol PTMG1000 is 1:2. During the reaction, the vacuum degree is maintained at 0.05 MPa. The water vapor in the water trap is released every 1 hour until the water content is less than 0.05 wt%. The mixture is cooled to room temperature (20°C) for standby;

[0109] The prepolymer M7 is prepared as follows: 50 parts by weight of the propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol is added to a reaction kettle, heated to 100°C, and vacuumed for 2 hours under stirring. After cooling to room temperature (20°C), 50 parts by weight of PM-300 is slowly added. The mixture is heated to 85°C and reacted for 3 hours. After cooling to room temperature (20°C), the mixture is filtered to obtain the prepolymer M7 (viscosity 1100 mPa·S at 25°C);

[0110] The polyurea resin is prepared as follows:

[0111] The 15 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 45 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 21 parts by weight of aromatic steric chain extender WANALINK 6200, 10 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 7.5 parts by weight of water absorbent A3 are stirred and mixed, the mixing rate is 800 rpm, the time is 30 min, after uniform mixing, the prepolymer M7 is added, wherein the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic steric chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of the prepolymer M7 are in a ratio of 1:2, to obtain a polyurea resin S7.

[0112] Example 8

[0113] The raw materials for preparing the polyurea resin S8 contain: 40 parts by weight of PM-300, 60 parts by weight of propylene carbonate-terminated linear polytetrahydrofuran ether terminal monohydric alcohol, 30 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 30 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts by weight of water absorbent A3, that is, the weight ratio of polymethylene polyphenyl isocyanate (PM-300) and capping agent (propylene carbonate-terminated linear polytetrahydrofuran ether terminal monohydric alcohol) is 1:1.5, the weight ratio of polyaspartic ester chain extender Desmophen NH XP-7068 and polyaspartic ester chain extender Desmophen NH 1420 is 1:1;

[0114] Preparation of propylene carbonate-terminated linear polytetrahydrofuran ether terminal monohydric alcohol:

[0115] A reaction kettle was charged with linear polytetrahydrofuran ether end group dihydric alcohol PTMG1000 with a weight average molecular weight of 1000, heated to 60°C, then propylene carbonate was added, heated to 120°C and reacted for 5h, the molar ratio of propylene carbonate to linear polytetrahydrofuran ether end group dihydric alcohol PTMG1000 was 1:2, the vacuum degree was maintained at 0.05MPa during the reaction, the water vapor in the water trap was discharged every 1h until the water content was less than 0.05wt%, and then cooled to room temperature (20°C) for standby;

[0116] Preparation of prepolymer M8: 60 parts by weight of propylene carbonate-terminated linear polytetrahydrofuran ether end group monohydric alcohol was added to a reaction kettle, heated to 100°C, vacuumed for 2h under stirring, and then slowly added 40 parts by weight of PM-300 after cooling to room temperature 20°C, heated to 85°C and reacted for 3h, then filtered out the material after cooling to room temperature 20°C, to obtain prepolymer M8 (viscosity 1040mPa·S at 25°C);

[0117] Preparation of polyurea resin:

[0118] 30 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 30 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric hindrance chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts of water absorbent A3 were stirred and mixed, the mixing rate was 800rpm, the mixing time was 30min, then the prepolymer M8 was added after uniform mixing, wherein the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic steric hindrance chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of prepolymer M8 was 1:2, to obtain polyurea resin S8.

[0119] Example 9

[0120] The raw materials for preparing the polyurea resin S9 contain: 60 parts by weight of PM-300, 30 parts by weight of propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol, 10 parts by weight of propylene carbonate-terminated linear polypropylene oxide ether monohydric alcohol, 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric hindrance chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wet dispersant BYKW980, 0.5 parts by weight of defoaming agent A-535, and 5.5 parts by weight of water absorber A3, i.e. the weight ratio of the polyfunctional isocyanate (PM-300) and the blocking agent (propylene carbonate-terminated linear polypropylene oxide ether monohydric alcohol and propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol) is 1:0.67, and the weight ratio of the polyaspartic ester chain extender Desmophen NH XP-7068 and the polyaspartic ester chain extender Desmophen NH 1420 is 1:2;

[0121] Preparation of propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol:

[0122] A linear polytetramethylene ether end group dihydric alcohol PTMG1000 with a weight average molecular weight of 1000 was added to a reaction kettle, heated to 60°C for incubation, then propylene carbonate was added, heated to 120°C for reaction for 5h, the molar ratio of propylene carbonate and linear polytetramethylene ether end group dihydric alcohol PTMG1000 was 1:2, the vacuum degree was maintained at 0.05MPa during the reaction, the water vapor in the water trap was released every 1h until the water content was less than 0.05wt%, and then cooled to room temperature (20°C) for standby;

[0123] Preparation of propylene carbonate-terminated linear polypropylene oxide ether monohydric alcohol:

[0124] A linear polypropylene oxide ether dihydric alcohol DL1000 with a weight average molecular weight of 1000 was added to a reaction kettle, heated to 60°C for incubation, then propylene carbonate was added, heated to 120°C for reaction for 5h, the molar ratio of propylene carbonate and linear polypropylene oxide ether dihydric alcohol DL1000 was 1:2, the vacuum degree was maintained at 0.05MPa during the reaction, the water vapor in the water trap was released every 1h until the water content was less than 0.05wt%, and then cooled to room temperature (20°C) for standby;

[0125] Preparation of prepolymer M9: 30 parts by weight of propylene carbonate-terminated linear polytetrahydrofuran ether monol and 10 parts by weight of propylene carbonate-terminated linear polyoxypropylene ether monol were added to a reaction kettle, heated to 100°C, vacuumized for 2h under stirring, cooled to room temperature 20°C, then 60 parts by weight of PM-300 was slowly added, heated to 85°C for 3h, cooled to room temperature 20°C, then filtered out the material, to obtain prepolymer M9 (viscosity 1180 mPa·S at 25°C);

[0126] Preparation of polyurea resin S9:

[0127] 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts of water absorbent A3 were stirred and mixed, the mixing rate was 800 rpm, the mixing time was 30 min, then the prepolymer M9 was added, wherein the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic steric chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of prepolymer M9 was 1:2, to obtain polyurea resin S9.

[0128] Example 10

[0129] The raw materials for preparing the polyurea resin S10 contain: 60 parts by weight of PM-400, 30 parts by weight of propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol, 10 parts by weight of propylene carbonate-terminated linear polypropylene oxide ether monohydric alcohol, 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric hindrance chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wet dispersant BYKW980, 0.5 parts by weight of defoaming agent A-535, and 5.5 parts by weight of water absorption agent A3, that is, the weight ratio of PM-400 and the blocking agent (propylene carbonate-terminated linear polypropylene oxide ether monohydric alcohol and propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol) is 1:0.67, and the weight ratio of polyaspartic ester chain extender Desmophen NH XP-7068 and polyaspartic ester chain extender Desmophen NH 1420 is 1:2;

[0130] Preparation of propylene carbonate-terminated linear polytetramethylene ether end group monohydric alcohol:

[0131] A linear polytetramethylene ether end group dihydric alcohol PTMG1000 with a weight average molecular weight of 1000 was added to a reaction kettle, heated to 60°C for incubation, then propylene carbonate was added, heated to 120°C for reaction for 5h, the molar ratio of propylene carbonate and linear polytetramethylene ether end group dihydric alcohol PTMG1000 was 1:2, the vacuum degree was maintained at 0.05MPa during the reaction, the water vapor in the water trap was discharged every 1h until the water content was less than 0.05wt%, and then cooled to room temperature (20°C) for standby;

[0132] Preparation of propylene carbonate-terminated linear polypropylene oxide ether monohydric alcohol:

[0133] A linear polypropylene oxide ether dihydric alcohol DL1000 with a weight average molecular weight of 1000 was added to a reaction kettle, heated to 60°C for incubation, then propylene carbonate was added, heated to 120°C for reaction for 5h, the molar ratio of propylene carbonate and linear polypropylene oxide ether dihydric alcohol DL1000 was 1:2, the vacuum degree was maintained at 0.05MPa during the reaction, the water vapor in the water trap was discharged every 1h until the water content was less than 0.05wt%, and then cooled to room temperature (20°C) for standby;

[0134] Preparation of prepolymer M10: 30 parts by weight of propylene carbonate-terminated linear polytetrahydrofuran ether monohydric alcohol and 10 parts by weight of propylene carbonate-terminated linear polyoxypropylene ether monohydric alcohol were added to a reaction kettle, warmed to 100°C, vacuumed for 2h under stirring, and after cooling to room temperature 20°C, 60 parts by weight of PM-400 was slowly added, warmed to 85°C and reacted for 3h, and after cooling to room temperature 20°C, the product was filtered to obtain prepolymer M10 (viscosity 1200 mPa·S at 25°C);

[0135] Preparation of polyurea resin:

[0136] 20 parts by weight of polyaspartic ester chain extender Desmophen NH XP-7068, 40 parts by weight of polyaspartic ester chain extender Desmophen NH 1420, 25 parts by weight of aromatic steric chain extender WANALINK 6200, 8 parts by weight of crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, 0.5 parts by weight of adhesion promoter AKN6000, 0.5 parts by weight of wetting dispersant BYK W980, 0.5 parts by weight of defoaming agent A-535 and 5.5 parts of water absorbent A3 were stirred and mixed, the mixing rate was 800 rpm, the time was 30 min, and after uniform mixing, prepolymer M10 was added, wherein the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic steric chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of prepolymer M10 was 1:2, to obtain polyurea resin S10.

[0137] Example 11

[0138] According to the manner of example 10, the implementation was carried out, except that the total weight of polyaspartic ester chain extender Desmophen NH XP-7068, polyaspartic ester chain extender Desmophen NH 1420, aromatic steric chain extender WANALINK 6200, crosslinking agent tetra(2-hydroxypropyl)ethylenediamine, adhesion promoter AKN6000, wetting dispersant BYK W980, defoaming agent A-535 and water absorbent A3 and the weight of prepolymer M10 was 1:4.

[0139] Example 12

[0140] The procedure of Example 10 was followed except that PM-400 was 90 parts by weight, propylene carbonate-capped linear polytetramethylene ether end-capped monool was 7.5 parts by weight, and propylene carbonate-capped linear polypropylene oxide ether monool was 2.5 parts by weight to obtain a prepolymer M12 (viscosity 890 mPa-s at 25°C).

[0141] Comparative Example 1

[0142] The procedure of Example 10 was followed except that the same weight of diphenylmethane diisocyanate (MDI-50) was used instead of polymethylene polyphenyl isocyanate.

[0143] Comparative Example 2

[0144] The procedure of Example 10 was followed except that the crosslinking agent tetra(2-hydroxypropyl)ethylenediamine was not added.

[0145] Comparative Example 3

[0146] The procedure of Example 10 was followed except that the end-capping agents propylene carbonate-capped linear polytetramethylene ether end-capped monool and propylene carbonate-capped linear polypropylene oxide ether monool were not added.

[0147] Test Example

[0148] The samples prepared in the examples and comparative examples were cured at 23±5°C for 7 days, and the solid content of the samples was determined according to the test procedure specified in 7.5 of GB / T 23446-2009, and the solid content of all samples was 100%, and then the performance of the samples was tested, and the test indexes were as follows:

[0149] (1) The gel time of the samples was determined according to the test procedure specified in 7.6 of GB / T 23446-2009, and the test results are shown in Table 1;

[0150] (2) The surface dry time of the samples was determined according to the test procedure specified in 7.7 of GB / T 23446-2009, and the test results are shown in Table 1;

[0151] (3) The tensile properties of the samples were determined according to the test procedure specified in GB / T 528-2009, and the test results are shown in Table 1;

[0152] (4) The tear strength of the samples was determined according to the test procedure specified in GB / T 529, and the test results are shown in Table 1;

[0153] (5) The adhesive strength of the samples was determined according to the test procedure specified in Chapter 7, Method A of GB / T 16777-2008, and the test results are shown in Table 1;

[0154] (6) The anti-gas explosion performance of the sample was determined according to the test procedure specified in T / CIESC 0019-2021, and the test results are shown in Table 1;

[0155] Table 1

[0156]

[0157] It can be seen from the results in Table 1 that the polyurea resin prepared by the application has good tensile strength and tear strength, good adhesion strength with the base body when applied in buildings, and excellent anti-gas explosion performance, meeting the performance of anti-explosion materials.

[0158] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application and fall within the protection scope of the application.

Claims

1. A composition for use with polyurea resin, characterized in that, The polyurea resin composition includes a prepolymer, a polyaspartic acid ester chain extender, an aromatic steric hindrance chain extender, a crosslinking agent, and optional additives. The prepolymer is obtained by polymerization of polymethylene polyphenyl isocyanate and a capping agent.

2. The composition for polyurea resin according to claim 1, characterized in that, The total weight ratio of polyaspartic acid ester chain extender, aromatic steric hindrance chain extender, crosslinking agent and optional additives to the prepolymer is 1:2 to 3.

3. The composition for polyurea resin according to claim 1 or 2, characterized in that, The capping agent is selected from one or more linear monohydric alcohols capped with benzyl alcohol, phenoxyethanol, and reactive diluent.

4. The composition for polyurea resin according to claim 3, characterized in that, The linear monohydric alcohols capped by the reactive diluent have a weight-average molecular weight of 100–3000.

5. The composition for polyurea resin according to claim 4, characterized in that, The linear monohydric alcohol is selected from one or more of linear polyoxypropylene ether-terminated monohydric alcohols, linear polytetrahydrofuran ether-terminated monohydric alcohols, linear polycaprolactone-terminated monohydric alcohols, and linear polycarbonate-terminated monohydric alcohols.

6. The composition for polyurea resin according to claim 1, characterized in that, The weight ratio of the polymethylene polyphenyl isocyanate to the capping agent is 1:0.25 to 1.

5.

7. The composition for polyurea resin according to any one of claims 1-6, characterized in that, The viscosity of the prepolymer is 300–3000 mPa·s.

8. The composition for polyurea resin according to claim 1, characterized in that, The polymethylene polyphenyl isocyanate has a functionality of 2.5–3, a viscosity of 150–700 mPa·s, and an NCO value of 30–32.

9. The composition for polyurea resin according to claim 1 or 8, characterized in that, The polymethylene polyphenyl isocyanate is selected from PM-200, PM-300 or PM-400.

10. The composition for polyurea resin according to claim 1, characterized in that, Based on the total weight of the polyaspartic ester chain extender, the aromatic steric hindrance chain extender, the crosslinking agent, and optional additives, the content of the polyaspartic ester chain extender is 30-89 wt%, the content of the aromatic steric hindrance chain extender is 10-40 wt%, the content of the crosslinking agent is 1-10 wt%, and the content of the additives is 0-9.5 wt%.

11. The composition for polyurea resin according to claim 1 or 10, characterized in that, The additives are selected from one or more of adhesion promoters, wetting and dispersing agents, defoamers, and water absorbents.

12. 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 1-11.

13. The method according to claim 12, characterized in that, The preparation method of the prepolymer includes: polymerizing polymethylene polyphenyl isocyanate and a capping agent, and then cooling and filtering the product.

14. The method according to claim 13, characterized in that, The conditions for the polymerization reaction include: a vacuum of -0.1 to 0.07 MPa, a temperature of 80 to 85°C, and a time of 2 to 4 hours.

15. The method according to claim 13 or 14, characterized in that, The capping agent is selected from one or more linear monohydric alcohols capped with benzyl alcohol, phenoxyethanol and reactive diluent; The method for preparing the linear monohydric alcohol capped with the reactive diluent includes: reacting the reactive diluent and the diol, and then cooling.

16. The method according to claim 15, characterized in that, The reaction conditions include: a vacuum of -0.1 to 0.07 MPa, a temperature of 100 to 130°C, and a time of 2 to 4 hours.

17. The method according to claim 15 or 16, characterized in that, The molar ratio of the reactive diluent to the diol is 1:2 to 4.

18. The method according to claim 17, characterized in that, The diol is selected from linear polyoxypropylene ether diol, linear polytetrahydrofuran ether diol, linear polycaprolactone diol, or linear polycarbonate diol.

19. The method according to claim 18, characterized in that, The weight-average molecular weight of the diol is 100 to 3000.

20. The polyurea resin prepared by the method according to any one of claims 12-19.

21. The application of the polyurea resin of claim 20 in explosion-proof materials.

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