Explosion-proof protective material and preparation method thereof

Abstract

The present invention relates to the field of protective material technology, in particular to the field of IPC C08G 18, and more specifically to an explosion-proof protective material and a preparation method thereof. The energy-absorbing material is composed of component A and component B: component A includes 50 to 75 parts of isocyanate, 25 to 55 parts of a first polyether polyol, and 5 to 15 parts of a diluent; component B includes 50 to 80 parts of a second polyether polyol, 30 to 55 parts of a polyether polyamine, 15 to 30 parts of an amine chain extender, and 5 to 20 parts of a color paste; the volume ratio of component A to component B is 1:(0.8-1.2). When the weight ratio of diethyltoluenediamine to dimethylthiotoluenediamine is 1:(0.2-0.6), the tensile strength (35MPa) and tear strength (120kN / m) of the material can be further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of protective materials, in particular to the field of IPC C08G 18, and more specifically to an anti-explosion protective material and a preparation method thereof. Background Art

[0002] Studies have shown that 80% of injuries and casualties caused by explosions are caused by debris generated by the explosion. Protecting equipment or buildings with a protective layer can improve the impact resistance of explosions by more than 20 times, reducing casualties within buildings by 50% under the same impact. There are many different blast-resistant materials, each with its own unique characteristics, but no one is perfect. For example, silicon carbide ceramic explosion-proof and bullet-proof cladding, commonly used on ships, is expensive and requires multiple pieces to be joined together, creating weak points at the joints and poor overall integrity. Blast-proof steel plates used in buildings are very heavy and inconvenient to install on unusually shaped structures. For structures like shelters, increasing the thickness of their metal walls significantly increases weight, compromising vehicle maneuverability. Polymer coatings offer a combination of low specific gravity and high protection, and have seen rapid development in recent years. Polyurethane coatings, with their high toughness and strength, hold great potential for application.

[0003] CN 108587438 A discloses an explosion-proof, energy-absorbing coating material, preparation method, and application thereof, belonging to the technical field of building protective materials. The invention discloses an explosion-proof, energy-absorbing coating material comprising a component A and a component B. Components A and B are prepared separately and then mixed using a two-component, high-temperature, high-pressure, impact-mixing airless spraying device. The mixed components are then sprayed onto a primer on the surface of a building substrate to form an explosion-proof, energy-absorbing coating. The coating improves the dynamic mechanical properties of protective structures under explosive loads and reduces the pressure within the protective structure caused by the explosion. However, the resulting coating material lacks sufficient toughness and strength. Summary of the Invention

[0004] The first aspect of the present invention provides an explosion-proof protective material. The energy-absorbing material consists of component A and component B, calculated by weight: component A includes 50 to 75 parts of isocyanate, 25 to 55 parts of a first polyether polyol, and 5 to 15 parts of a diluent; component B includes 50 to 80 parts of a second polyether polyol, 30 to 55 parts of a polyether polyamine, 15 to 30 parts of an amine chain extender, and 5 to 20 parts of a color paste; the volume ratio of component A to component B is 1:(0.8-1.2).

[0005] The isocyanate includes at least one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

[0006] Preferably, the isocyanate includes at least one of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate.

[0007] More preferably, the isocyanate includes one of MDI-50 and MDI-100, both of which are purchased from Wanhua Chemical.

[0008] More preferably, the isocyanate includes MDI-50, purchased from Wanhua Chemical.

[0009] The first polyether polyol includes one of polytetramethylene glycol and polyethylene glycol.

[0010] Preferably, the first polyether polyol comprises polytetramethylene ether glycol, and the molecular weight of the polytetramethylene ether glycol is 600-5000.

[0011] Preferably, the molecular weight of the polytetramethylene ether glycol includes two types: 650 and 2000.

[0012] Preferably, the weight ratio of the polytetramethylene ether glycol with a molecular weight of 650 to that with a molecular weight of 2000 is 1:(1.5-2).

[0013] More preferably, the weight ratio of polytetramethylene ether glycol with a molecular weight of 650 to that with a molecular weight of 2000 is 1:1.6.

[0014] The polytetramethylene ether glycol with a molecular weight of 650 and a molecular weight of 2000 are respectively P650 and P2000, and are purchased from Green Union Chemical Technology Co., Ltd.

[0015] The diluent includes one or more of dibutyl phthalate, dioctyl phthalate, propylene carbonate, ethylene carbonate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, dimethyl carbonate or dimethoxyethyl phthalate.

[0016] Preferably, the diluent comprises propylene carbonate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and the weight ratio of the propylene carbonate to the 2,2,4-trimethyl-1,3-pentanediol diisobutyrate is 1:(2-4).

[0017] Further preferably, the diluent comprises propylene carbonate (CAS: 108-32-7) and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (CAS: 846-50-0), and the weight ratio of the propylene carbonate to the 2,2,4-trimethyl-1,3-pentanediol diisobutyrate is 1:3.5.

[0018] Preferably, the second polyether polyol includes polytetramethylene ether glycol with a molecular weight of 1000, model P1000, purchased from Green Union Chemical Technology Co., Ltd.

[0019] The applicant's research has found that adding polytetramethylene ether glycol bis(p-aminobenzoate) with a molecular weight of 500-1500 can effectively improve the tensile strength and tensile elastic modulus of the material. The substituents of polytetramethylene ether glycol bis(p-aminobenzoate) are symmetrically arranged on the main chain, which increases the main chain spacing and can interact with the hydrogen bonds between polyether polyols, thereby increasing the degree of hydrogen bonding and promoting an increase in the degree of microphase separation, thereby improving the strength.

[0020] The polyether polyamine includes polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 500-1500.

[0021] Preferably, the polyether polyamine comprises polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 650 and 1000, and the weight ratio of the polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 650 and 1000 is (0.2-0.5):1.

[0022] Further preferably, the polyether polyamine includes polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 650 and 1000, the weight ratio of the polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 650 and 1000 is 1:4, and the polytetramethylene ether glycol bis-p-aminobenzoate is purchased from Zhangjiagang Yarui Chemical Co., Ltd.

[0023] The amine chain extender includes one or more of diethyltoluenediamine, bis-sec-butylaminodiphenylmethane, dimethylthiotoluenediamine, diaminodicyclohexylmethane, isophoronediamine, and trimethylhexanediamine.

[0024] The applicant has discovered that the amine chain extender includes diethyltoluenediamine and dimethylthiotoluenediamine. A weight ratio of 1:(0.2-0.6) of dimethylthiotoluenediamine to diethyltoluenediamine can improve the tensile strength and tear strength of the material, presumably contributing to the formation of a large structure and increased crosslinking density. Furthermore, dimethylthiotoluenediamine has a relatively slow reaction rate, and when mixed with diethyltoluenediamine, it imparts good surface leveling properties to the material, improving surface properties and confining blasting fragments and dust within the coating, providing significant safety during building demolition. Furthermore, the specific amine chain extender can reduce the reaction rate, extending the gel time to over 2 minutes, resulting in superior interlayer adhesion during multi-pass spraying, eliminating the need for an interface agent. Furthermore, the longer gel time facilitates the placement of fiber mesh cloth as needed during construction, resulting in a stronger bond.

[0025] The present invention also utilizes polytetramethylene ether glycol bis-p-aminobenzoate with molecular weights of 650 and 1000 in a weight ratio of (0.2-0.5):1, balancing the viscosity of the resin, ensuring consistency in the viscosities of components A and B, thereby ensuring consistent spray pressure. This facilitates spraying applications on military equipment and building exteriors. Because it is less prone to foaming than polyether polyols and has a slower reaction speed than the amino polyethers commonly used in polyureas, it also addresses the problem of foaming during construction in high humidity, often caused by a slower reaction speed of polyurethane, thereby maintaining material strength.

[0026] Preferably, the amine chain extender includes diethyltoluenediamine and dimethylthiotoluenediamine, and the weight ratio of the dimethylthiotoluenediamine to diethyltoluenediamine is 1:(0.2-0.6).

[0027] More preferably, the amine chain extender includes diethyltoluenediamine and dimethylthiotoluenediamine, and the weight ratio of the dimethylthiotoluenediamine to diethyltoluenediamine is 1:0.4.

[0028] More preferably, the diethyltoluenediamine, model number: E100, and the dimethylthiotoluenediamine, model number: E300, are both purchased from Albemarle Corporation in the United States.

[0029] The color paste includes at least one of titanium dioxide, calcium carbonate, diatomaceous earth, glass fiber, clay, barite, and carbon black.

[0030] Preferably, the color paste includes titanium dioxide and diatomaceous earth, and the weight ratio of the titanium dioxide to diatomaceous earth is 1:(0.2-0.5).

[0031] Further preferably, the color paste includes titanium dioxide and diatomaceous earth, and the weight ratio of the titanium dioxide to diatomaceous earth is 1:0.4.

[0032] Preferably, the titanium dioxide is purchased from Lingshou County Hongrun Mineral Products Processing Plant, and the diatomaceous earth has a mesh size of 325 and is purchased from Lingshou County Hongrun Mineral Products Processing Plant.

[0033] The spray-on polyurethane coating of the present invention is similar to the spray-on pure polyurea coating, both employing a dedicated two-component high-pressure airless sprayer. Pure polyurea spray-on coatings, which utilize an isocyanate semi-prepolymer, an ammonia-based chain extender, and an amino polyether, react quickly, curing in just a few seconds. This results in poor interlayer adhesion, and multiple spray coats often require additional application of an interface agent, which is time-consuming and labor-intensive. Furthermore, the types of amino polyethers available for pure polyurea spray-on coatings are limited.

[0034] A second aspect of the present invention provides a method for preparing an explosion-proof protective material, comprising the following steps:

[0035] S1, heating the first polyether polyol to 100-120°C with stirring, dehydrating under vacuum at 0.05-0.07 MPa for 1-2 hours, and adding isocyanate after cooling to 20-30°C, reacting, cooling to 50-70°C, adding diluent, stirring evenly, and discharging after 0.2-0.8 hours to obtain component A;

[0036] S2, add the raw materials of component B, mix evenly at 20-30°C, and stir for 1-2 hours to obtain component B;

[0037] S3, spraying component A and component B through a spraying device, and curing and forming.

[0038] The volume ratio of component A to component B is 1:(1-1.2).

[0039] Preferably, the weight ratio of the isocyanate to the first polyether polyol is (1.25-2):1.

[0040] Preferably, the isocyanate group content of component A is 15-20%.

[0041] Preferably, the volume ratio of component A to component B is 1:1.

[0042] The reaction temperature is 60-80° C., and the reaction time is 1.5-2.5 h.

[0043] Preferably, the reaction temperature is 70° C. and the reaction time is 2 h.

[0044] Beneficial effects:

[0045] 1. The material prepared by the present invention has an excellent ability to attenuate overpressure shock waves. It has high mechanical strength and good toughness, and can provide effective protection when subjected to explosion shock waves. It can be applied to military equipment, vehicles, and ships to protect them from damage, especially preventing the splashing of bricks and other building materials that could cause secondary damage to personnel. It can be used in armored vehicle chassis to effectively improve the vehicle's resistance to mine explosions. It can also be used in military shelters to effectively prevent damage to the shelters from explosion shock waves and fragments.

[0046] Used in small special ships, it can effectively enhance the damage to underwater explosion shock waves.

[0047] 2. Adding polytetramethylene ether glycol bis(p-aminobenzoate) with a molecular weight of 500-1500 can effectively improve the tensile strength (35MPa) and tensile elastic modulus (300MPa) of the material.

[0048] 3. When the weight ratio of dimethylthiotoluenediamine to diethyltoluenediamine is 1:(0.2-0.6), the tensile strength (35MPa) and tear strength (120kN / m) of the material can be further improved, while the reaction rate is reduced, so that the gel time can be extended to more than 2 minutes.

[0049] 4. The weight ratio of polytetramethylene ether glycol bis-p-aminobenzoate with molecular weight of 650 and 1000 is (0.2-0.5):1, which can balance the viscosity of the resin and make the viscosity of components A and B consistent, thereby making the spraying pressure consistent, which is beneficial for spraying equipment to carry out spraying construction on military equipment and building exteriors.

[0050] 5. The color paste includes titanium dioxide and diatomaceous earth, and the weight ratio of titanium dioxide and diatomaceous earth is 1: (0.2-0.5), which can increase the hardness of the material to above 85 (Shore A) and the yield strength is higher than 13MPa.

[0051] 6. Controlling the isocyanate group content of component A to 15-20% can improve the tensile strength (35MPa) and tear strength (120kN / m) of the material.

[0052] 7. The spray polyurethane anti-explosion coating of the present invention has the advantages of simple construction, low specific gravity, good overall molding, and high cost performance, and can play its advantages in many application fields. DETAILED DESCRIPTION

[0053] Example 1

[0054] An anti-explosion protective material, wherein the energy absorbing material is composed of component A and component B, calculated by weight: component A is 65.4 parts of isocyanate, 43.6 parts of a first polyether polyol, and 12 parts of a diluent; component B is 60 parts of a second polyether polyol, 45 parts of a polyether polyamine, 20 parts of an amine chain extender, and 10 parts of a color paste;

[0055] The isocyanate is MDI-50, purchased from Wanhua Chemical.

[0056] The first polyether polyol is polytetramethylene ether diol; the molecular weight of the polytetramethylene ether diol is 650 and 2000; the weight ratio of the polytetramethylene ether diol with a molecular weight of 650 and a molecular weight of 2000 is 1:1.6; the models of the polytetramethylene ether diol with a molecular weight of 650 and a molecular weight of 2000 are P650 and P2000, respectively, and both are purchased from Green Union Chemical Technology Co., Ltd.

[0057] The diluent is propylene carbonate (CAS: 108-32-7) and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (CAS: 846-50-0), and the weight ratio of the propylene carbonate to the 2,2,4-trimethyl-1,3-pentanediol diisobutyrate is 1:3.5.

[0058] The second polyether polyol is polytetramethylene ether glycol with a molecular weight of 1000, model P1000, purchased from Green Union Chemical Technology Co., Ltd.

[0059] The polyether polyamine is polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 650 and 1000, and the weight ratio of the polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 650 and 1000 is 1:4. The polytetramethylene ether glycol bis-p-aminobenzoate is purchased from Zhangjiagang Yarui Chemical Co., Ltd.

[0060] The amine chain extender is diethyltoluenediamine and dimethylthiotoluenediamine, and the weight ratio of diethyltoluenediamine to dimethylthiotoluenediamine is 1:0.4; the diethyltoluenediamine is model: E100, and the dimethylthiotoluenediamine is model: E300, both of which are purchased from Albemarle Corporation of the United States.

[0061] The color paste is titanium dioxide and diatomaceous earth, and the weight ratio of the titanium dioxide and diatomaceous earth is 1:0.4.

[0062] The titanium dioxide was purchased from Lingshou County Hongrun Mineral Products Processing Plant, and the diatomaceous earth had a mesh size of 325 and was purchased from Lingshou County Hongrun Mineral Products Processing Plant.

[0063] A method for preparing an explosion-proof protective material comprises the following steps:

[0064] S1, heating the first polyether polyol to 110°C with stirring, dehydrating under vacuum at 0.05 MPa for 1.5 hours, cooling to 25°C, adding isocyanate, reacting at 70°C for 2 hours, cooling to 60°C, adding diluent, stirring evenly, and discharging after 0.5 hours to obtain component A;

[0065] S2, add the raw materials of component B, stir at 25°C for 1.5h to obtain component B;

[0066] S3, spraying component A and component B through a spraying device, and curing and forming.

[0067] The isocyanate group content of the A component is 15.1%.

[0068] The weight ratio of component A to component B is 1:1.

[0069] Example 2

[0070] The specific implementation is the same as that of Example 1; the difference is that in Example 2: the weight ratio of diethyltoluenediamine to dimethylthiotoluenediamine is 1:0.2.

[0071] Example 3

[0072] The specific implementation is the same as that of Example 1; the difference is that in Example 3: the weight ratio of polytetramethylene ether glycol bis-p-aminobenzoate with molecular weights of 650 and 1000 is 0.4:1.

[0073] Example 4

[0074] The specific implementation is the same as that of Example 1; the difference is that in Example 4: component A comprises 70 parts of isocyanate and 40 parts of the first polyether polyol.

[0075] The isocyanate group content of the A component is 16.3%.

[0076] Example 5

[0077] The specific implementation is the same as that of Example 1; the difference is that in Example 5: component A comprises 70 parts of isocyanate and 30 parts of the first polyether polyol.

[0078] The isocyanate group content of the A component is 18.0%.

[0079] Comparative Example 1

[0080] The specific implementation is the same as Example 1; the difference is that in Comparative Example 1: the weight ratio of diethyltoluenediamine to dimethylthiotoluenediamine is 1:1.

[0081] Comparative Example 2

[0082] The specific implementation is the same as that of Example 1; the difference is that in Comparative Example 2: the molecular weight of polytetramethylene ether glycol bis-p-aminobenzoate is 1000.

[0083] Comparative Example 3

[0084] The specific implementation is the same as Example 1; the difference is that in Comparative Example 3: the weight ratio of polytetramethylene ether glycol bis-p-aminobenzoate with molecular weights of 650 and 1000 is 0.8:1.

[0085] Comparative Example 4

[0086] The specific implementation is the same as Example 1; the difference is that in Comparative Example 4: Component A contains 60 parts of isocyanate and 60 parts of the first polyether polyol.

[0087] The isocyanate group content of the A component is 12.1%.

[0088] Performance testing methods

[0089] The performance tests were carried out in the embodiments and comparative examples, and the test data are listed in Table 1.

[0090] Performance test data

[0091] Table 1

[0092]

[0093]

Claims

1. An explosion-proof protective material, characterized in that: The invention comprises component A and component B, wherein the raw materials of component A include 50-75 parts of isocyanate, 25-55 parts of first polyether polyol, and 5-15 parts of diluent; the raw materials of component B include 50-80 parts of second polyether polyol, 30-55 parts of polyether polyamine, 15-30 parts of amine chain extender, and 5-20 parts of color paste; the volume ratio of component A to component B is 1:(0.8-1.2); The first polyether polyol includes polytetramethylene glycol, the molecular weight of the polytetramethylene glycol includes two types: 650 and 2000, and the weight ratio of the polytetramethylene glycol with a molecular weight of 650 to that with a molecular weight of 2000 is 1:(1.5-2); The polyether polyamine includes polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 650 and 1000, and the weight ratio of the polytetramethylene ether glycol bis-p-aminobenzoate with a molecular weight of 650 and 1000 is (0.2-0.5):1; The amine chain extender comprises diethyltoluenediamine and dimethylthiotoluenediamine, and the weight ratio of the diethyltoluenediamine to dimethylthiotoluenediamine is 1:(0.2-0.6).

2. The explosion-proof protective material according to claim 1, characterized in that: The isocyanate includes at least one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

3. The explosion-proof protective material according to claim 2, characterized in that: The isocyanate includes at least one of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate.

4. The explosion-proof protective material according to claim 1, characterized in that: The diluent includes one or more of dibutyl phthalate, dioctyl phthalate, propylene carbonate, ethylene carbonate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, dimethyl carbonate or dimethoxyethyl phthalate.

5. A method for preparing explosion-proof protective material according to claim 1, characterized in that: The following steps are involved: S1, heating the first polyether polyol to 100-120°C with stirring, dehydrating under vacuum at 0.05-0.07 MPa for 1-2 hours, and adding isocyanate after cooling to 20-30°C, reacting, cooling to 50-70°C, adding diluent, stirring evenly, and discharging after 0.2-0.8 hours to obtain component A; S2, add the raw materials of component B, mix evenly at 20-30°C, and stir for 1-2 hours to obtain component B; S3, spraying component A and component B through a spraying device, and curing and forming.

6. The method for preparing explosion-proof protective material according to claim 5, characterized in that: The volume ratio of component A to component B is 1:(1-1.2).

7. The method for preparing explosion-proof protective material according to claim 5, characterized in that: The reaction temperature is 60-80° C., and the reaction time is 1.5-2.5 h.

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