阅读说明：本技术 一种防爆抗冲击纤维增强聚脲复合材料及其制备方法和应用 (Explosion-proof impact-resistant fiber-reinforced polyurea composite material and preparation method and application thereof ) 是由 卢卫 党文义 白永忠 王林 于 2020-05-25 设计创作，主要内容包括：本发明提供一种防爆抗冲击纤维增强聚脲复合材料及其制备方法和应用,该复合材料包括纤维格栅和涂覆在纤维格栅上的聚脲,所述聚脲包括A、B两个组分,以重量计,所述A组分为由含有40～80份异氰酸酯、60～100份聚四氢呋喃醚多元醇、5～10份三官能度多元醇的原料经聚合反应得到的半预聚物组分；以重量计,所述B组分含有5～15份扩链剂、30～50份端氨基聚醚和5～10份助剂。本发明的纤维增强聚脲复合材料总厚度可达3～5mm,所述复合材料使纤维格栅、聚脲形成化学结合,同时存在宏观互穿结构,由此使得本发明的复合材料在具备较好柔韧性的条件下,保持较高的基材附着力、拉伸强度、撕裂强度和抗冲击性能。(The invention provides an explosion-proof and impact-resistant fiber-reinforced polyurea composite material and a preparation method and application thereof, the composite material comprises a fiber grating and polyurea coated on the fiber grating, wherein the polyurea comprises A, B two components, and the component A is a semi-prepolymer component obtained by polymerization reaction of raw materials containing 40-80 parts by weight of isocyanate, 60-100 parts by weight of polytetrahydrofuran ether polyol and 5-10 parts by weight of trifunctional polyol; the component B comprises, by weight, 5-15 parts of a chain extender, 30-50 parts of an amino-terminated polyether and 5-10 parts of an auxiliary agent. The total thickness of the fiber reinforced polyurea composite material can reach 3-5mm, the composite material enables the fiber grating and the polyurea to form chemical combination, and a macroscopic interpenetrating structure exists, so that the composite material disclosed by the invention keeps higher base material adhesion, tensile strength, tearing strength and impact resistance under the condition of better flexibility.)

1. An explosion-proof and impact-resistant fiber-reinforced polyurea composite material comprises a fiber grid and polyurea coated on the fiber grid, wherein the polyurea comprises A, B two components, and the component A is a semi-prepolymer obtained by prepolymerization of raw materials containing 40-80 parts by weight of isocyanate, 60-100 parts by weight of polytetrahydrofuran ether polyol and 5-10 parts by weight of trifunctional polyol; the component B comprises, by weight, 5-15 parts of a chain extender, 30-50 parts of amine-terminated polyether and 5-10 parts of an auxiliary agent.

2. The composite of claim 1, wherein the substrate adhesion is 8-12MPa, the tensile strength is 30-50MPa, the tear strength is 50-120MPa, and the impact resistance is 40-100 MPa.

3. The composite of claim 1, wherein the fiber reinforced polyurea composite has a thickness of 3-5 mm; and/or the fiber grid and the polyurea are compounded in a layered form.

4. The composite according to claim 1 or 2, wherein the fiber lattice has a thickness of 0.5-1.0mm and a pore size of 1.0-3.0 mm.

5. The composite material according to claim 1 or 2, wherein the fiber lattice is woven in cross and cross direction from 0.5-1.0mm thick fiber filaments.

6. The composite of claim 1 or 2, wherein the fiber composition of the fiber lattice is one or more of Kevlar fibers, glass fibers, carbon fibers and spandex fibers.

7. The composite material according to claim 1 or 2, wherein the fiber grid comprises: the fiber material and the silane coupling agent loaded on the fiber material, wherein the weight ratio of the silane coupling agent to the fiber material is 2-10: 100.

8. the composite material of claim 7, wherein the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, and gamma- (methacryloyloxy) propyltrimethoxysilane.

9. The composite material according to claim 1 or 2,

the weight ratio of the component A to the component B is (0.8-1.2) to 1, and the weight ratio of the fiber grating to the polyurea is 0.1-0.5: 1.

10. the composite material according to claim 1 or 2, wherein, in the A component,

the isocyanate is composed of two or more than two of bifunctional isocyanate and/or polyfunctional isocyanate, and at least contains one of bifunctional isocyanate and polyfunctional isocyanate; preferably, the difunctional isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate; preferably, the polyfunctional isocyanate is one or more of polyphenyl polymethylene polyisocyanate, 4' -triphenylmethane triisocyanate.

11. The composite material according to claim 1 or 2, wherein the polytetrahydrofuran ether polyol in the A component is one or more of polytetrahydrofuran ether polyols with molecular weight of 1000-2000-.

12. The composite material of claim 1 or 2, wherein in the component A, the trifunctional polyol is one or more of polypropylene oxide ether triol with molecular weight of 100-1000 and polyethylene oxide ether triol with molecular weight of 100-1000.

13. The composite material according to claim 1 or 2, wherein in the B component,

the chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diamine, 3' -dichloro-4, 4' -diphenyl methane diamine and isophorone diamine.

14. The composite material according to claim 1 or 2, wherein in the B component,

the amino-terminated polyether is one or more of polytetramethylene ether glycol di-p-aminobenzoate and amino-terminated polyoxypropylene ether.

15. The composite material according to claim 1 or 2, wherein in the B component,

the auxiliary agent is two or more of defoamer BYK-A530, defoamer BYK-141, defoamer BYK-1770, defoamer EFKA2020, antioxidant 264, antioxidant 1010 and antioxidant 1076, and at least comprises one of defoamer and antioxidant.

16. A method of preparing an explosion proof and impact resistant fiber reinforced polyurea composite as claimed in any one of claims 1 to 15, comprising:

the preparation steps of the component A comprise:

carrying out stepwise polymerization reaction on raw materials containing 40-80 parts of isocyanate, 60-100 parts of polytetrahydrofuran ether polyol and 5-10 parts of trifunctional polyol to obtain a component A;

the preparation steps of the component B comprise: mixing 5-15 parts of chain extender, 30-50 parts of amine-terminated polyether and 5-10 parts of auxiliary agent to obtain a component B;

and spraying the component A and the component B on a base material, and placing the fiber grating on the sprayed base material for complementary coating until the fiber grating is fully coated.

17. The production method according to claim 16, wherein,

in the component A, the isocyanate is composed of two or more than two of bifunctional isocyanate and/or polyfunctional isocyanate, and at least contains one of bifunctional isocyanate and polyfunctional isocyanate;

the preparation steps of the component A comprise:

firstly, dehydrating polytetrahydrofuran ether polyol and trifunctional polyol under reduced pressure until the water content is not more than 0.1 wt%;

secondly, reacting the dehydrated trifunctional polyalcohol and the bifunctional isocyanate in a molar ratio of 1:3-3.15 in a three-necked bottle at normal temperature for 1-2 h;

adding polytetrahydrofuran ether polyol with the same mole as the bifunctional isocyanate, and reacting for 1-2h at the temperature of 50-80 ℃;

adding bifunctional isocyanate with the same mole as that in the step (II) again, and reacting for 1-2h at the temperature of 50-80 ℃;

adding the polyfunctional isocyanate.

18. The production method according to claim 16 or 17, wherein the A-component and the B-component are sprayed onto a substrate, the fiber lattice is placed before the sprayed substrate,

coating or impregnating the fiber grating with a diluted silane coupling agent, and drying to obtain a modified fiber grating;

preferably, the silane coupling agent is diluted by an alcohol solvent, and the volume ratio of the silane coupling agent to the alcohol solvent is (20-30): 100, respectively; preferably the alcohol is ethanol and/or butanol.

19. The production method according to claim 16 or 17, wherein the spraying is performed by mechanical spraying, the volume ratio of the a component to the B component is (0.8-1.2):1, and the gel time after spraying is 2-5 min.

20. Use of the explosion proof impact resistant fiber reinforced polyurea composite according to any one of claims 1 to 15 as a building coating in a building material.

Technical Field

The invention belongs to the field of composite materials, and particularly relates to an explosion-proof impact-resistant fiber-reinforced polyurea composite material as well as a preparation method and application thereof.

Background

The polyurea material has the characteristics of high strength, high toughness, excellent impact resistance, low cost, convenient construction and the like, and the polyurea-based composite material reinforced by the materials such as fibers is an ideal material for explosion prevention and impact resistance, and can be widely applied to the engineering fields of explosion prevention of buildings, military equipment protection, explosion prevention, impact resistance and the like of refining enterprises, explosion prevention of civil mines, dams, piers and the like.

Chinese patent application 201611082325 discloses an explosion-proof impact-resistant polyurea coating and a preparation method thereof, and provides a graphene-reinforced polyurea coating. However, the technology does not show the impact resistance and the substrate adhesion of the material.

Chinese patent application 201710404555 discloses a Kevlar fiber cloth reinforced polyurea composite material and a preparation method thereof, and the technology is to immerse the Kevlar fiber cloth which is subjected to chemical treatment into a polyurea elastomer to obtain an impact-resistant composite material with extremely high strength and toughness. The composite material is prefabricated and molded, and is matched with an adhesive and corresponding measures to be attached to base materials such as concrete, metal and the like when being applied in construction in certain fields. And the tearing property, the impact resistance and the adhesion force with the base material of the material are not reflected by the technology.

Disclosure of Invention

The invention aims to provide a fiber reinforced polyurea composite material which can still keep higher base material adhesive force, tensile strength, tearing strength and impact resistance under the condition of better flexibility, and a preparation method and application thereof.

In order to achieve the above object, in a first aspect, the present invention provides an explosion-proof and impact-resistant fiber-reinforced polyurea composite material, which comprises a fiber grid and polyurea coated on the fiber grid, wherein the polyurea comprises A, B two components, and the component a is a semi-prepolymer component obtained by prepolymerization of a raw material comprising 40 to 80 parts by weight of isocyanate, 60 to 100 parts by weight of polytetrahydrofuran ether polyol, and 5 to 10 parts by weight of trifunctional polyol; the component B comprises, by weight, 5-15 parts of a chain extender, 30-50 parts of an amino-terminated polyether and 5-10 parts of an auxiliary agent.

Preferably, the substrate adhesion is 8-12MPa, the tensile strength is 30-50MPa, the tear strength is 50-120MPa and the impact resistance is 40-100 MPa.

Preferably, the thickness of the fiber-reinforced polyurea composite material is 3-5 mm; preferably, the fiber lattice and the polyurea are compounded in a layered form.

Preferably, the thickness of the fiber grating is 0.5-1.0mm, and the aperture is 1.0-3.0 mm.

Preferably, the fiber grating is formed by weaving fiber yarns with the thickness of 0.5-1.0mm in a longitudinal and transverse mode.

Preferably, the fiber component of the fiber grid is one or more of kevlar fiber, glass fiber, carbon fiber and spandex fiber.

Preferably, the fiber grating includes: the fiber material and the silane coupling agent loaded on the fiber material, wherein the weight ratio of the silane coupling agent to the fiber material is 2-10: 100, respectively; preferably, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.

Preferably, the first and second electrodes are formed of a metal,

the weight ratio of the component A to the component B is (0.8-1.2) to 1, and the weight ratio of the fiber grating to the polyurea is 0.1-0.5: 1;

in the component A:

the isocyanate is composed of two or more than two of bifunctional isocyanate and/or polyfunctional isocyanate, and at least contains one of bifunctional isocyanate and polyfunctional isocyanate; preferably, the difunctional isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate; preferably, the polyfunctional isocyanate is one or more of polyphenyl polymethylene polyisocyanate, 4' -triphenylmethane triisocyanate; and/or

The polytetrahydrofuran ether polyol is one or more of polytetrahydrofuran ether polyols with the molecular weight of 1000-2000; and/or

The tri-functionality polyol is one or more of polypropylene oxide ether triol with the molecular weight of 100-1000 and polyethylene oxide ether triol with the molecular weight of 100-1000;

in the component B, the component B is a mixture of,

the chain extender is one or more of diethyl toluenediamine, dimethyl sulfenyl toluenediamine, N ' -dialkyl methyl diamine, 3' -dichloro-4, 4' -diphenyl methane diamine and isophorone diamine;

the amino-terminated polyether is one or more of polytetramethylene ether glycol di-p-aminobenzoate and amino-terminated polyoxypropylene ether;

the auxiliary agent is two or more of defoamer BYK-A530, defoamer BYK-141, defoamer BYK-1770, defoamer EFKA2020, antioxidant 264, antioxidant 1010 and antioxidant 1076, and at least comprises one of defoamer and antioxidant.

In a second aspect, the present invention provides a method for preparing the explosion-proof and impact-resistant fiber-reinforced polyurea composite material, comprising:

the preparation steps of the component A comprise:

carrying out stepwise polymerization reaction on raw materials containing 40-80 parts of isocyanate, 60-100 parts of polytetrahydrofuran ether polyol and 5-10 parts of trifunctional polyol to obtain a component A;

the preparation steps of the component B comprise: mixing 5-15 parts of chain extender, 30-50 parts of amine-terminated polyether and 5-10 parts of auxiliary agent to obtain a component B;

and spraying the component A and the component B on a base material, and placing the fiber grating on the sprayed base material for complementary coating until the fiber grating is fully coated.

Preferably, in the A component, the isocyanate is composed of two or more of difunctional isocyanate and/or polyfunctional isocyanate, and at least contains one of difunctional isocyanate and polyfunctional isocyanate;

the preparation steps of the component A comprise:

firstly, dehydrating polytetrahydrofuran ether polyol and trifunctional polyol under reduced pressure until the water content is not more than 0.1 wt%;

secondly, reacting the dehydrated trifunctional polyalcohol and the bifunctional isocyanate in a molar ratio of 1:3-3.15 in a three-necked bottle at normal temperature for 1-2 h;

adding polytetrahydrofuran ether polyol with the same mole as the bifunctional isocyanate, and reacting for 1-2h at the temperature of 50-80 ℃;

adding bifunctional isocyanate with the same mole as that in the step (II) again, and reacting for 1-2h at the temperature of 50-80 ℃;

adding the polyfunctional isocyanate.

Preferably, the A component and the B component are sprayed on a substrate, the fiber grating is arranged on the sprayed substrate,

coating or impregnating the fiber grating with a diluted silane coupling agent, and drying to obtain a modified fiber grating;

preferably, the silane coupling agent is diluted by an alcohol solvent, and preferably, the volume ratio of the silane coupling agent to the alcohol solvent is (20-30): 100, respectively; preferably the alcohol is ethanol and/or butanol.

Preferably, the spraying is carried out by mechanical spraying, the volume ratio of the component A to the component B is (0.8-1.2):1, and the gel time after spraying is 2-5 min.

According to a third aspect of the invention, the invention provides the use of the explosion-proof impact-resistant fiber-reinforced polyurea composite according to the invention as a building coating in a building material.

The total thickness of the fiber reinforced polyurea composite material can reach 3-5mm, the composite material enables the fiber grating and the polyurea to form chemical combination, and a macroscopic interpenetrating structure exists, so that the composite material disclosed by the invention keeps higher base material adhesion, tensile strength, tearing strength and impact resistance under the condition of better flexibility.

Detailed Description

The invention provides an explosion-proof and impact-resistant fiber-reinforced polyurea composite material which comprises a fiber grating and polyurea coated on the fiber grating, wherein the polyurea comprises A, B two components, and the component A is a semi-prepolymer component obtained by prepolymerization of raw materials containing 40-80 parts by weight of isocyanate, 60-100 parts by weight of polytetrahydrofuran ether polyol and 5-10 parts by weight of trifunctional polyol; the component B comprises, by weight, 5-15 parts of a chain extender, 30-50 parts of an amino-terminated polyether and 5-10 parts of an auxiliary agent.

The total thickness of the fiber reinforced polyurea composite material can reach 3-5mm, the composite material enables the fiber grating and the polyurea to form chemical combination, and a macroscopic interpenetrating structure exists, so that the composite material disclosed by the invention keeps higher base material adhesion, tensile strength, tearing strength and impact resistance under the condition of better flexibility.

According to a preferred embodiment of the present invention, the fiber-reinforced polyurea composite material has a thickness of 3 to 5 mm. The preferable parameters can further improve the flexibility of the composite material, and keep higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the invention, the substrate adhesion is from 8 to 12MPa, the tensile strength is from 30 to 50MPa, the tear strength is from 50 to 120MPa and the impact resistance is from 40 to 100 MPa.

According to a preferred embodiment of the present invention, the fiber grating and the polyurea are compounded in a layered form, and more preferably, the fiber grating and the polyurea are chemically bonded and compounded in a layered form. The preferable parameters can further improve the flexibility of the composite material, and keep higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the present invention, the thickness of the fiber grating is 0.5 to 1.0 mm. The preferable parameters can further improve the flexibility of the composite material, and keep higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the present invention, the pore diameter is 1.0 to 3.0 mm. The preferable parameters can further improve the flexibility of the composite material, and keep higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the present invention, the fiber grating is formed by vertically and horizontally weaving fiber filaments with a thickness of 0.5 to 1.0 mm.

Any conventional fiber composition may be used in the present invention, and according to a preferred embodiment of the present invention, the fiber composition of the fiber grating is one or more of kevlar fiber, glass fiber, carbon fiber, and spandex fiber.

According to a preferred embodiment of the invention, the fiber grid comprises: a fiber material and a silane coupling agent supported on the fiber material.

According to a preferred embodiment of the invention, the weight ratio of silane coupling agent to the fibrous material is from 2 to 10: 100. the optimization can further improve the flexibility of the composite material, and maintain higher substrate adhesion, tensile strength, tearing strength and impact resistance.

Conventional silane coupling agents may be used in the present invention, including but not limited to one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.

According to a preferred embodiment of the present invention, the weight ratio of the A component to the B component is (0.8-1.2): 1. The preferable parameters can further improve the flexibility of the composite material, and keep higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the invention, the weight ratio of the fiber grid to the polyurea is between 0.1 and 0.5: 1. the preferable parameters can further improve the flexibility of the composite material, and keep higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the invention, in component a: the isocyanate is composed of two or more of difunctional isocyanate and/or polyfunctional isocyanate, and contains at least one of difunctional isocyanate and polyfunctional isocyanate. The preferred embodiment can further improve the flexibility of the composite material, and maintain higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the present invention, the difunctional isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate.

According to a preferred embodiment of the invention, the polyfunctional isocyanate is one or more of polyphenyl polymethylene polyisocyanate, 4' -triphenylmethane triisocyanate.

The preferred embodiment can further improve the flexibility of the composite material, and maintain higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the present invention, the polytetrahydrofuran ether polyol is one or more of polytetrahydrofuran ether polyols having a molecular weight of 1000 to 2000. The preferred embodiment can further improve the flexibility of the composite material, and maintain higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the present invention, the trifunctional polyol is one or more of a polyoxypropylene ether triol having a molecular weight of 100 to 1000 and a polyoxyethylene ether triol having a molecular weight of 100 to 1000. The preferred embodiment can further improve the flexibility of the composite material, and maintain higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the present invention, in the B component, the chain extender may be a commonly used chain extender including, but not limited to, one or more of diethyltoluenediamine, dimethylthiotoluenediamine, N ' -dialkylmethyldiamine, 3' -dichloro-4, 4' -diphenylmethanediamine, and isophoronediamine.

According to a preferred embodiment of the invention, in the component B, the amino-terminated polyether comprises but is not limited to one or more of polytetramethylene ether glycol di-p-aminobenzoate and amino-terminated polyoxypropylene ether; the preferred embodiment can further improve the flexibility of the composite material, and maintain higher substrate adhesion, tensile strength, tearing strength and impact resistance.

According to a preferred embodiment of the invention, the polytetramethylene ether glycol bis-P-aminobenzoate is for example P1000, P650.

According to a preferred embodiment of the invention, the amino-terminated polyoxypropylene ether is, for example, D2000, D400, T3000, T5000, T430.

According to a preferred embodiment of the invention, in the component B, the auxiliary agent can be a corresponding functional auxiliary agent commonly used in the field, and for the invention, two or more of defoaming agent BYK-A530, defoaming agent BYK-141, defoaming agent BYK-1770, defoaming agent EFKA2020, antioxidant 264, antioxidant 1010 and antioxidant 1076 are preferred, and at least one of the defoaming agent and the antioxidant is contained. The preferred embodiment can further improve the flexibility of the composite material, and maintain higher substrate adhesion, tensile strength, tearing strength and impact resistance.

The composite material with the composition and the properties can achieve the aim of the invention, and has no special requirement on the preparation method, and aiming at the invention, the invention preferably provides a preparation method of the explosion-proof and impact-resistant fiber reinforced polyurea composite material, which comprises the following steps:

the preparation steps of the component A comprise:

carrying out stepwise polymerization reaction on raw materials containing 40-80 parts of isocyanate, 60-100 parts of polytetrahydrofuran ether polyol and 5-10 parts of trifunctional polyol to obtain a component A;

the preparation steps of the component B comprise: mixing 5-15 parts of chain extender, 30-50 parts of amine-terminated polyether and 5-10 parts of auxiliary agent to obtain a component B;

and spraying the component A and the component B on a base material, and placing the fiber grating on the sprayed base material for complementary coating until the fiber grating is fully coated.

According to the preferred embodiment of the invention, the steps of spraying the A component and the B component on a base material, placing the fiber grating on the sprayed base material for coating, and repeatedly laying a new fiber grating and coating again to form a multi-layer composite structure until the coating is full comprise:

cleaning and wiping the surface of a base material to be constructed; polyurea is coated on a cleaned base material by adopting a spraying process (the volume ratio of coating A to B is 1 to 1) in a thickness of 0.5-0.7mm, a pretreated fiber grid is flatly pasted on the polyurea coating, and the edge of the fiber is reduced by 5-10 mm compared with the edge of the polyurea coating (the edge of the fiber is subjected to sealing treatment, so that the edge of the fiber is prevented from being exposed, and the performance of a composite material is not influenced); carrying out second polyurea spraying until the fiber grating is fully coated; rotating the second layer of fiber grating clockwise by 45 degrees, flatly pasting the second layer of fiber grating on the second polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; carrying out a third polyurea spraying till the fiber grating is fully coated; repeating the steps, and spraying three to five times to enable the total thickness of the fiber reinforced polyurea composite material to reach 3-5 mm.

According to a preferred embodiment of the present invention, in the a component, the isocyanate is composed of two or more of bifunctional isocyanate and/or polyfunctional isocyanate, and contains at least either of bifunctional isocyanate and polyfunctional isocyanate;

preferably, the preparation steps of the A component comprise:

firstly, dehydrating polytetrahydrofuran ether polyol and trifunctional polyol under reduced pressure until the water content is not more than 0.1 wt%;

secondly, reacting the dehydrated trifunctional polyalcohol and the bifunctional isocyanate in a molar ratio of 1:3-3.15 in a three-necked bottle at normal temperature for 1-2 h;

adding polytetrahydrofuran ether polyol with the same mole as the bifunctional isocyanate, and reacting for 1-2h at the temperature of 50-80 ℃;

adding the bifunctional isocyanate with the same mole again, and reacting for 1-2h at the temperature of 50-80 ℃;

adding the polyfunctional isocyanate.

According to a preferred embodiment of the invention, the A component and the B component are sprayed on a substrate, and before the fiber grating is placed on the sprayed substrate, the fiber grating is coated with a diluted silane coupling agent or is dried after being impregnated to obtain the modified fiber grating.

According to the preferred embodiment of the present invention, the fiber grating is pre-treated by painting or dipping with a diluted silane coupling agent, and then air-dried in a natural environment for at least 12 hours or more.

According to a preferred embodiment of the present invention, the silane coupling agent is diluted by an alcohol solvent.

According to a preferred embodiment of the present invention, the volume ratio of the silane coupling agent to the alcohol solvent is (20 to 30): 100.

according to a preferred embodiment of the invention, the alcohol is ethanol and/or butanol.

According to the preferred embodiment of the invention, the spraying is carried out by mechanical spraying, and the volume ratio of the component A to the component B is (0.8-1.2): 1.

According to the preferred embodiment of the invention, the gel time after spraying is 2-5 min.

According to a third aspect of the invention, the invention provides the use of the explosion-proof impact-resistant fiber-reinforced polyurea composite according to the invention as a building coating in a building material.

The total thickness of the fiber reinforced polyurea composite material can reach 3-5mm, the composite material enables the fiber grating and the polyurea to form chemical combination, and a macroscopic interpenetrating structure exists, so that the composite material disclosed by the invention keeps higher base material adhesion, tensile strength, tearing strength and impact resistance under the condition of better flexibility.

According to a preferred embodiment of the invention, the explosion-proof and impact-resistant fiber-reinforced polyurea composite material is formed by compounding fiber grids and polyurea in a layered form. The thickness of the fiber grating is 0.5-1.0mm, the aperture is 1.0-3.0mm, and the fiber grating is coated with a diluted silane coupling agent or dried in the air for at least 12 hours in the natural environment after dipping pretreatment. The polyurea comprises A, B two components, wherein the component A is a semi-prepolymer component obtained by step-by-step polymerization reaction of 40-80 parts of isocyanate, 60-100 parts of polytetrahydrofuran ether polyol and 5-10 parts of trifunctional polyol; the component B comprises 5-15 parts of chain extender, 30-50 parts of amine-terminated polyether and 5-10 parts of auxiliary agent. The total thickness of the fiber reinforced polyurea composite material can reach 3-5 mm.

According to the preferred embodiment of the invention, the fiber grating is formed by weaving fiber filaments with the thickness of 0.5-1.0mm vertically and horizontally, the aperture of the grating is controlled to be 1.0-3.0mm, and the thickness of the grating is controlled to be 0.5-1.0 mm. The component is preferably one of Kevlar fiber, glass fiber, carbon fiber and spandex fiber.

According to a preferred embodiment of the present invention, the silane coupling agent is composed of one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, and gamma- (methacryloyloxy) propyltrimethoxysilane. Diluting by ethanol, butanol or a mixture thereof, wherein the volume ratio of the silane coupling agent to the ethanol, the butanol or the mixture thereof is (20-30): 100.

The polyurea comprises A, B two components, the mechanical spraying process is adopted for construction, the volume ratio of A, B two components is (0.8-1.2):1, and the gel time after spraying is 2-5 min. The polyurea A component is a semi-prepolymer component obtained by reacting 40-80 parts of isocyanate, 60-100 parts of polytetrahydrofuran ether polyol and 5-10 parts of trifunctional polyol. The component B comprises 5-15 parts of chain extender, 30-50 parts of amine-terminated polyether and 5-10 parts of auxiliary agent.

According to a preferred embodiment of the present invention, the isocyanate is composed of two or more of difunctional and polyfunctional isocyanates and contains at least one of the difunctional and polyfunctional isocyanates.

According to a preferred embodiment of the present invention, the difunctional isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate.

According to a preferred embodiment of the invention, the polyfunctional isocyanate is one or more of polyphenyl polymethylene polyisocyanate, 4' -triphenylmethane triisocyanate.

According to a preferred embodiment of the present invention, the polytetrahydrofuran ether polyol is one or two of polytetrahydrofuran ether polyols having a molecular weight of 1000 to 2000.

According to a preferred embodiment of the present invention, the trifunctional polyol is one or more of a polyoxypropylene ether triol having a molecular weight of 100 to 1000 and a polyoxyethylene ether triol having a molecular weight of 100 to 1000.

According to a preferred embodiment of the invention, the component A is synthesized by the following process:

firstly, dehydrating polytetrahydrofuran ether polyol and trifunctional polyol at 120 ℃ under reduced pressure until the water content is not more than 0.1%;

secondly, reacting the dehydrated trifunctional polyalcohol and the bifunctional isocyanate in a molar ratio of 1:3-3.15 in a three-necked bottle at normal temperature for 1-2 h;

adding polytetrahydrofuran ether polyol with the same mole as the bifunctional isocyanate, and reacting for 1-2h at the temperature of 50-80 ℃;

adding the bifunctional isocyanate with the same mole again, and reacting for 1-2h at the temperature of 50-80 ℃;

adding certain amount of polyfunctional isocyanate.

According to a preferred embodiment of the present invention, the chain extender is one or two of diethyltoluenediamine, dimethylthiotoluenediamine, N ' -dialkylmethyldiamine, 3' -dichloro-4, 4' -diphenylmethanediamine, isophoronediamine.

According to a preferred embodiment of the invention, the amino-terminated polyether is one or two of polytetramethylene ether glycol bis-P-aminobenzoate (P1000, P650), amino-terminated polyoxypropylene ether (D2000, D400, T3000, T5000, T430).

According to the preferred embodiment of the invention, the auxiliary agent is one or two of defoaming agent BYK-A530, defoaming agent BYK-141, defoaming agent BYK-1770, defoaming agent EFKA2020, antioxidant 264, antioxidant 1010 and antioxidant 1076.

According to a preferred embodiment of the invention, the step of spraying the A component and the B component on the base material, and the step of placing the fiber grating on the sprayed base material for complementary coating until full coating comprises the following steps: cleaning and wiping the surface of a base material to be constructed; spraying polyurea on a cleaned substrate by adopting a spraying process (for example, the volume ratio of the coating A to the coating B is 1:1), coating the polyurea on the cleaned substrate in an example of a thickness of 0.5mm, and immediately flatly pasting the pretreated fiber grating on the polyurea coating, wherein the edge of the fiber is preferably reduced by 5-10 mm compared with the edge of the polyurea coating; carrying out second polyurea spraying until the fiber grating is fully coated; rotating the second layer of fiber grating clockwise by 45 degrees, flatly pasting the second layer of fiber grating on the second polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; carrying out a third polyurea spraying till the fiber grating is fully coated; rotating the third layer of fiber grating clockwise by 45 degrees, flatly pasting the fiber grating on the third polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; and finally, performing fourth spraying to enable the total thickness of the fiber reinforced polyurea composite material to reach 3 mm.

The present invention will be described in further detail with reference to examples. The following components are in parts by weight.

Example 1

γ - (2, 3-glycidoxy) propyltrimethoxysilane: the solution with 20:100 (volume ratio) of ethanol is coated on a Kevlar fiber grid with the thickness of 0.5mm and the pore diameter of 2 mm. And after treatment, the mixture is air-dried for 12 hours in a natural environment.

Polyurea A component prepolymer synthesis step:

PTMG1000 (polytetrahydrofuran ether polyol with molecular weight of 1000) and GP303 (polyether triol with molecular weight of 300) are respectively dehydrated for 2 hours under reduced pressure at 120 ℃;

the following parts are parts by weight.

② reacting 6 parts of dehydrated GP303 and 10.5 parts of TDI-80/20 (toluene diisocyanate) in a three-necked bottle at normal temperature for 1 h;

③ adding 60 parts of dehydrated PTMG1000, and reacting for 1h at 60 ℃;

fourthly, 10.5 parts of TDI-80/20 is added again to react for 1 hour at the temperature of 60 ℃;

fifthly, adding 29 parts of PM200 (polyphenyl polymethylene polyisocyanate).

Preparing a polyurea component B:

6 parts of E-300 (dimethylthiotoluenediamine), 10 parts of amino-terminated polyether P650, 30 parts of amino-terminated polyether T-3000, 1 part of defoaming agent BYK-A530 and 4 parts of antioxidant 1010, and dispersing for 20min in a high-speed stirrer at a speed of 1000r/min until the components are uniformly mixed.

The construction steps are as follows:

cleaning and wiping the surface of a base material to be constructed; polyurea is coated on a cleaned base material in a thickness of 0.5mm by adopting a spraying process (the volume ratio of coating A to coating B is 1 to 1), a pretreated fiber grid is immediately and flatly pasted on the polyurea coating, and the edge of the fiber is reduced by 5-10 mm compared with the edge of the polyurea coating; carrying out second polyurea spraying until the fiber grating is fully coated; rotating the second layer of fiber grating clockwise by 45 degrees, flatly pasting the second layer of fiber grating on the second polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; carrying out a third polyurea spraying till the fiber grating is fully coated; rotating the third layer of fiber grating clockwise by 45 degrees, flatly pasting the fiber grating on the third polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; and finally, performing fourth spraying to enable the total thickness of the fiber reinforced polyurea composite material to reach 3 mm.

The composite performance criteria are shown in table 1 below.

TABLE 1

Tensile strength	32MPa
		Elongation percentage	170％
Adhesion (base material: concrete)	9.0MPa (concrete failure)
		Gel time	2min
Tear strength	75MPa
		Impact strength	>49MPa

Example 2

γ - (2, 3-glycidoxy) propyltrimethoxysilane: the butanol (30: 100) solution was applied to a carbon fiber grid having a thickness of 1mm and a pore diameter of 1 mm. And after treatment, the mixture is air-dried for 12 hours in a natural environment.

Polyurea A component prepolymer synthesis step:

PTMG2000 (polytetrahydrofuran ether polyol with molecular weight of 2000) and GP306 (polyether triol with molecular weight of 600) are respectively dehydrated for 2 hours under reduced pressure at 120 ℃;

secondly, 9.6 parts of dehydrated GP306 and 12 parts of MDI100 (diphenylmethane diisocyanate) are reacted for 1 hour at normal temperature in a three-necked bottle;

③ adding 96 parts of dehydrated PTMG2000, and reacting for 1h at 70 ℃;

fourthly, 12 parts of MDI100 are added again to react for 1 hour at the temperature of 70 ℃;

add 46 parts of PM 200.

Preparing a polyurea component B:

6 parts of E-300, 16 parts of amino terminated polyether P1000, 24 parts of D2000, 1 part of defoamer EFKA2020, and 5 parts of antioxidant 264. Dispersing in a high speed mixer at 1000r/min for 20min to mix evenly.

The construction steps are as follows:

cleaning and wiping the surface of a base material to be constructed; polyurea is coated on a cleaned base material by adopting a spraying process with the thickness of 0.5mm, a pretreated fiber grid is immediately and flatly pasted on the polyurea coating, and the edge of the fiber is reduced by 5-10 mm compared with the edge of the polyurea coating; carrying out second polyurea spraying until the fiber grating is fully coated; rotating the second layer of fiber grating clockwise by 45 degrees, flatly pasting the second layer of fiber grating on the second polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; carrying out a third polyurea spraying till the fiber grating is fully coated; rotating the third layer of fiber grating clockwise by 45 degrees, flatly pasting the fiber grating on the third polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; performing a fourth polyurea spraying until the fiber grating is fully coated; rotating the fourth layer of fiber grating clockwise by 45 degrees, flatly pasting the fourth layer of fiber grating on the fourth polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; and finally, performing fifth spraying to enable the total thickness of the fiber reinforced polyurea composite material to reach 5 mm.

The performance indexes of the composite material are shown in the following table 2 (the volume ratio of the coating A to the coating B is 1:1)

TABLE 2

Tensile strength	36MPa
		Elongation percentage	160％
Adhesion (base material: concrete)	9.5MPa (concrete failure)
		Gel time	3.5min
Tear strength	79MPa
		Impact strength	>49MPa

The impact-resistant fiber reinforced polyurea composite material has high strength, good toughness, better adhesive force, low requirements on equipment production and construction equipment, and quick and convenient construction.

Example 3

Gamma-aminopropyltriethoxysilane: the solution with 20:100 (volume ratio) of ethanol is coated on a Kevlar fiber grid with the thickness of 0.5mm and the pore diameter of 3 mm. And after treatment, the mixture is air-dried for 12 hours in a natural environment.

Polyurea A component prepolymer synthesis step:

dehydrating PTMG1000 and GP303 respectively at 120 ℃ for 2h under reduced pressure;

secondly, 6 parts of dehydrated GP303 and 10.5 parts of TDI-80/20 are reacted for 1 hour at normal temperature in a three-necked bottle;

③ adding 60 parts of dehydrated PTMG1000, and reacting for 2 hours at 50 ℃;

fourthly, 10.5 parts of TDI-80/20 is added again to react for 1 hour at the temperature of 80 ℃;

fifthly, adding 29 parts of PM 200.

Preparing a polyurea component B:

6 parts of E-300, 10 parts of P650, 30 parts of T-3000, 1 part of defoaming agent BYK-A530 and 4 parts of antioxidant 1010, and dispersing for 20min in a high-speed stirrer at 1000r/min until the mixture is uniformly mixed.

The construction steps are as follows:

cleaning and wiping the surface of a base material to be constructed; polyurea is coated on a cleaned base material in a thickness of 0.7mm by adopting a spraying process (the volume ratio of coating A to coating B is 1 to 1), a pretreated fiber grid is immediately and flatly pasted on the polyurea coating, and the edge of the fiber is reduced by 5-10 mm compared with the edge of the polyurea coating; carrying out second polyurea spraying until the fiber grating is fully coated; rotating the second layer of fiber grating clockwise by 45 degrees, flatly pasting the second layer of fiber grating on the second polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; carrying out a third polyurea spraying till the fiber grating is fully coated; rotating the third layer of fiber grating clockwise by 45 degrees, flatly pasting the fiber grating on the third polyurea coating, and keeping the fiber edge to be reduced by 5-10 mm compared with the polyurea coating edge; and finally, performing fourth spraying to enable the total thickness of the fiber reinforced polyurea composite material to reach 4 mm.

The composite performance index is as follows in table 3:

TABLE 3

Tensile strength	35MPa
		Elongation percentage	160％
Adhesion (base material: concrete)	9.2MPa (concrete failure)
		Gel time	3min
Tear strength	72MPa
		Impact strength	>49MPa

Example 4

Prepared according to the method of example 3 except that the fiber grating was coated with a diluted silane coupling agent, wherein propylene glycol was used for dilution in an amount corresponding to the amount of ethanol, and the other conditions were the same.

The composite performance index is as follows in table 4:

TABLE 4

Tensile strength	33MPa
		Elongation percentage	155％
Adhesion (base material: concrete)	9.0MPa (concrete failure)
		Gel time	3min
Tear strength	70MPa
		Impact strength	>47MPa

Example 5

Prepared according to the method of example 1 except that,

polyurea A component prepolymer synthesis step:

PTMG1000 (polytetrahydrofuran ether polyol with molecular weight of 1000) and GP303 (polyether triol with molecular weight of 300) are respectively dehydrated for 2 hours under reduced pressure at 120 ℃;

the following parts are parts by weight.

6 parts of dehydrated GP303 and 10.5 parts of PM200 (polyphenyl polymethylene polyisocyanate) are reacted for 1 hour at normal temperature in a three-necked bottle;

③ adding 60 parts of dehydrated PTMG1000, and reacting for 1h at 60 ℃;

fourthly, 10.5 parts of TDI-80/20 is added again to react for 1 hour at the temperature of 60 ℃;

fifthly, adding 29 parts of PM200 (polyphenyl polymethylene polyisocyanate).

The composite performance criteria are given in table 5 below.

TABLE 5

Tensile strength	27MPa
		Elongation percentage	166％
Adhesion (base material: concrete)	8.0MPa (concrete failure)
		Gel time	2min
Tear strength	73MPa
		Impact strength	>46MPa

Example 6

Prepared according to the method of example 1 except that,

polyurea A component prepolymer synthesis step:

PTMG1000 (polytetrahydrofuran ether polyol with molecular weight of 1000) and GP303 (polyether triol with molecular weight of 300) are respectively dehydrated for 2 hours under reduced pressure at 120 ℃;

the following parts are parts by weight.

② reacting 6 parts of dehydrated GP303 and 10.5 parts of TDI-80/20 (toluene diisocyanate) in a three-necked bottle at normal temperature for 1 h;

③ adding 60 parts of dehydrated PTMG1000, and reacting for 1h at 60 ℃;

fourthly, 10.5 parts of TDI-80/20 is added again to react for 1 hour at the temperature of 60 ℃;

adding 29 portions of TDI-80/20 (toluene diisocyanate).

The composite performance criteria are shown in table 6 below.

TABLE 6

Tensile strength	28MPa
		Elongation percentage	165％
Adhesion force(base material: concrete)	9.0MPa (concrete failure)
		Gel time	2min
Tear strength	71MPa
		Impact strength	>45MPa

Comparative example 1

Prepared according to the method of example 1 except that,

polyurea A component prepolymer synthesis step:

PTMG1000 (polytetrahydrofuran ether polyol with molecular weight of 1000) and GP303 (polyether triol with molecular weight of 300) are respectively dehydrated for 2 hours under reduced pressure at 120 ℃;

the following parts are parts by weight.

② 31 parts of dehydrated GP303 is added into 85 parts of dehydrated PTMG1000, and the reaction is carried out for 1h under the condition of 60 ℃.

The composite performance criteria are given in table 7 below.

TABLE 7

Comparative example 2

Prepared according to the method of example 1 except that,

polyurea A component prepolymer synthesis step:

dehydrating GP303 (polyether triol with molecular weight of 300) at 120 ℃ under reduced pressure for 2 h;

the following parts are parts by weight.

② reacting 36 parts of dehydrated GP303 and 20.5 parts of TDI-80/20 (toluene diisocyanate) in a three-necked bottle at normal temperature for 1 h;

③ adding 20.5 parts of TDI-80/20 again, and reacting for 1 hour at the temperature of 60 ℃;

(iv) 39 parts of PM200 (polyphenyl polymethylene polyisocyanate) is added.

The composite performance criteria are given in table 8 below.

TABLE 8

Tensile strength	28MPa
		Elongation percentage	170％
Adhesion (base material: concrete)	7.5MPa (concrete failure)
		Gel time	2min
Tear strength	45MPa
		Impact strength	>36MPa

Comparative example 3

The procedure of example 1 was followed except that the polyurea A component prepolymer synthesis procedure:

dehydrating PTMG1000 (polytetrahydrofuran ether polyol, molecular weight 1000) at 120 deg.C under reduced pressure for 2 h;

the following parts are parts by weight.

Adding 13.5 parts of TDI-80/20 (toluene diisocyanate) into 63 parts of dehydrated PTMG1000, and reacting for 1h at 60 ℃ in a three-necked bottle;

adding 10.5 parts of TDI-80/20 again, and reacting for 1h at 60 ℃;

29 parts of PM200 (polyphenyl polymethylene polyisocyanate) are added.

The composite performance criteria are given in table 9 below.

TABLE 9

Tensile strength	25.5MPa
		Elongation percentage	170％
Adhesion (base material: concrete)	7MPa (concrete failure)
		Gel time	2min
Tear strength	44MPa
		Impact strength	>34MPa

The composite material resin and the reinforcing material form a macroscopic interpenetrating structure, and can still keep higher base material adhesive force, tensile strength, tearing strength and impact resistance under the condition of better flexibility.

Although the invention described and claimed herein has been described in considerable detail by way of example, it should be understood by those skilled in the art that the invention described and claimed herein may be practiced in other embodiments than those specifically described for purposes of illustration. The spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.

In summary, the preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.