Polyurethane barrier explosion suppression material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of explosion suppression materials, in particular to a polyurethane barrier explosion suppression material and a preparation method and application thereof. The invention discloses a polyurethane barrier explosion suppression material, which is prepared from the following raw materials in parts by weight: 50 to 80 parts of polyether polyol, 50 to 80 parts of polyester polyol, 0.5 to 0.8 part of catalysts, 6 to 10 parts of toluene diisocynate, 6 to 10 parts of foaming agents and 1 to 2 parts of stabilizing agents. The polyurethane blocking and explosion suppression material is obtained by compounding the polyether polyol and the polyester polyol and selecting the composite catalyst, and the polyurethane blocking and explosion suppression material can maintain good performance in a wide temperature range, especially has more balanced performance in the aspects of hydrolysis resistance and chemical corrosion resistance, and has good application prospects. The problems that an existing barrier explosion suppression material is prone to softening under the high-temperature condition, insufficient in mechanical strength, limited in explosion suppression effect and the like are successfully solved.

Description

Technical Field

[0001] The invention relates to the technical field of explosion suppression materials, and in particular to polyurethane barrier explosion suppression materials and a preparation method and application thereof. Background Art

[0002] At present, the existing barrier explosion suppression materials on the market mainly include silicone rubber, polyurethane foam, modified polyolefin and other types. These materials meet the needs of different application scenarios to a certain extent, especially in the fields of tank trucks and aviation fuel tanks, showing good application prospects. However, the existing barrier explosion suppression materials still have some shortcomings and need further optimization and improvement.

[0003] Existing barrier explosion suppression materials are prone to softening or decomposition under high temperature conditions, resulting in a decrease in their barrier properties. In addition, these materials are not mechanically strong enough and are easily damaged when impacted or squeezed, affecting their reliability in long-term use. At the same time, existing barrier explosion suppression materials can inhibit the spread of flames to a certain extent, but under extreme conditions, their barrier effect is still limited and cannot completely prevent the occurrence of explosions.

[0004] To this end, the present application provides a polyurethane barrier explosion suppression material and a preparation method and application thereof. Summary of the invention

[0005] The present application provides a polyurethane barrier explosion suppression material and a preparation method and application thereof. The polyurethane barrier explosion suppression material is obtained by compounding polyether polyols and polyester polyols and selecting a composite catalyst. The polyurethane barrier explosion suppression material can maintain good performance in a wide temperature range, especially in terms of hydrolysis resistance and chemical corrosion resistance. It is more balanced and successfully solves the problems of existing barrier explosion suppression materials being easy to soften under high temperature conditions, insufficient mechanical strength, and limited explosion suppression effect. The polyurethane barrier explosion suppression material described in the present application shows excellent effects in terms of hydrolysis resistance, fuel resistance, flame retardancy, and explosion suppression performance, and has broad application prospects, especially in flammable environments such as tank trucks and aviation fuel tanks.

[0006] The technical solution adopted by this application to solve its technical problem is:

[0007] In a first aspect, the present application provides a polyurethane barrier explosion suppression material, comprising the following raw materials in parts by weight:

[0008] 50-80 parts of polyether polyol, 50-80 parts of polyester polyol, 0.5-0.8 parts of catalyst, 6-10 parts of toluene diisocyanate, 6-10 parts of foaming agent, and 1-2 parts of stabilizer.

[0009] In one or more technical solutions, the method for preparing the polyester polyol comprises the following steps:

[0010] Under nitrogen protection, dimer fatty acid, adipic acid and neopentyl glycol are put into a reactor and fully mixed; the reactor is heated, the heating rate is controlled, the generated water is gradually evaporated, and the temperature of the distillation column head on the reactor is controlled to be 95-100°C;

[0011] When the temperature in the reactor rises to 160-170°C, keep it at 160-170°C for 1-2 hours, then slowly raise the temperature to 200°C, remove the fractionation column when water stops coming out of the fractionation column head, continue the reaction until the acid value drops below 30, then cool it; add dibutyltin dilaurate, continue to heat to 220°C and keep it for reaction until the acid value drops below 1, then stop the reaction to obtain polyester polyol;

[0012] The total molar ratio of the dimerized fatty acid and adipic acid to the molar ratio of the neopentyl glycol is 1.24:1; the molar ratio of the dimerized fatty acid to adipic acid is 0.25:1.

[0013] In one or more technical solutions, the CAS number of the dimer fatty acid is 61788-89-4.

[0014] In the present application, due to the strong hydrophobicity of dimer acid, the ester bonds in the polyurethane elastomer formed by the polyester polyol are in a hydrophobic environment with extremely low water content, which effectively slows down the hydrolysis reaction; therefore, the polyurethane elastomer formed by the above polyester polyol is immersed in hot water at 100°C for 14 days, and the tensile strength retention rate is high (the retention rate is greater than 99%), showing good water resistance. At a tensile modulus of 300%, there is no tensile hardening phenomenon, showing good elasticity and impact resistance.

[0015] In one or more technical solutions, the method for preparing the polyether polyol comprises the following steps:

[0016] In a nitrogen environment, trihydroxyethyl isocyanurate and a double metal cyanide complex catalyst are put into a reactor; then epichlorohydrin is added into the reactor, and the reaction is carried out at 1-2MPa and 130-140°C for 2-3h; after the reaction is completed, the unreacted epichlorohydrin is removed to obtain a polyether polyol.

[0017] Specifically, the polyether polyol of the present application has a large number of methylene chloride side groups on the molecular chain, which makes the polyether polyol have excellent flame retardancy and corrosion resistance, good oil resistance and ozone resistance, and is suitable for use in special environments such as oil fields and underwater. Since the ether bonds in the molecular structure of the polyether polyol have low cohesive energy, the polyurethane material prepared from the polyether polyol has good low-temperature compliance.

[0018] In one or more technical solutions, the molar ratio of trihydroxyethyl isocyanurate to epichlorohydrin is 1:1.2.

[0019] In one or more technical solutions, the dosage of the double metal cyanide complex catalyst is 0.1-0.15% by weight of trishydroxyethyl isocyanurate.

[0020] In one or more technical solutions, the catalyst is composed of DBU and thiourea in a weight ratio of 4:1.

[0021] In one or more technical solutions, the blowing agent is water.

[0022] In one or more technical solutions, the stabilizer is dimethyl silicone oil.

[0023] In a second aspect, the present application provides a method for preparing the polyurethane barrier explosion suppression material according to the first aspect, comprising the following steps:

[0024] S1. Preparation of polyester polyols

[0025] Under nitrogen protection, dimer fatty acid, adipic acid and neopentyl glycol are put into a reactor and fully mixed; the reactor is heated, the heating rate is controlled, the generated water is gradually evaporated, and the temperature of the distillation column head on the reactor is controlled to be 95-100°C;

[0026] When the temperature in the reactor rises to 160-170°C, keep it at 160-170°C for 1-2 hours, then slowly raise the temperature to 200°C, remove the fractionation column when water stops coming out of the fractionation column head, continue the reaction until the acid value drops below 30, then cool it; add dibutyltin dilaurate, continue to heat to 220°C and keep it for reaction until the acid value drops below 1, then stop the reaction to obtain polyester polyol;

[0027] S2. Preparation of polyether polyols

[0028] In a nitrogen environment, trihydroxyethyl isocyanurate and a double metal cyanide complex catalyst are put into a reactor; then epichlorohydrin is added into the reactor, and the reaction is carried out at 1-2MPa and 130-140°C for 2-3h; after the reaction is completed, the unreacted epichlorohydrin is removed to obtain a polyether polyol.

[0029] S3. Mixing and foaming

[0030] Take 50-80 parts of polyether polyol, 50-80 parts of polyester polyol and 6-10 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat up to 85°C under a nitrogen environment, and react at 85°C for 2-3 hours; then add 0.5-0.8 parts of catalyst, 6-10 parts of foaming agent and 1-2 parts of stabilizer into the reactor, mix thoroughly, heat up to 150-155°C, and react for 5-6 hours; after the reaction is completed, cool to room temperature to obtain a barrier explosion suppression material.

[0031] In a third aspect, the present application provides an application of a polyurethane barrier explosion suppression material, wherein the polyurethane barrier explosion suppression material described in the first aspect or the polyurethane barrier explosion suppression material prepared by the preparation method described in the second aspect is used as a filling material in a fuel tank.

[0032] The beneficial effects of this application are:

[0033] The polyurethane barrier explosion suppression material described in the present application combines the advantages of polyether and polyester. For example, polyether polyol has good hydrolysis resistance, while polyester polyol has good chemical corrosion resistance. Therefore, the polyurethane barrier explosion suppression material has a more balanced performance in terms of hydrolysis resistance and chemical resistance. For example, the low-temperature flexibility provided by polyether polyol and the heat resistance provided by polyester polyol enable the polyurethane barrier explosion suppression material to maintain good performance in a wide temperature range. The polyurethane barrier explosion suppression material has good adaptability in different environments and can maintain stable performance under changing environmental conditions. DETAILED DESCRIPTION

[0034] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0035] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0036] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple, respectively.

[0037] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0038] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0039] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass described in the embodiment description of the present application can be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.

[0040] The terms "first" and "second" are used only for descriptive purposes to distinguish objects such as substances from each other, and should not be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features.

[0041] Preparation Example 1

[0042] The preparation method of polyester polyol comprises the following steps:

[0043] Prepare a reactor with a fractionating column, electric stirring, thermometer and nitrogen protection device, introduce nitrogen to remove the air in the system, and fully mix the dimer fatty acid, adipic acid and neopentyl glycol; heat, and when the temperature rises to about 140°C, water begins to come out. At this time, control the heating rate so that the generated water is gradually evaporated. Control the distillation column head temperature of the fractionating column to 95-100°C;

[0044] When the temperature rises to 160°C, keep the temperature for 2 hours, then slowly raise the temperature to 200°C, remove the fractionation column when water stops coming out of the fractionation column head, continue the reaction until the acid value drops below 30, and then cool; add dibutyltin dilaurate, continue to heat to 220°C and keep the temperature for reaction until the acid value drops below 1, to obtain polyester polyol;

[0045] The total molar ratio of the dimerized fatty acid and adipic acid to the molar ratio of the neopentyl glycol is 1.24:1; the molar ratio of the dimerized fatty acid to adipic acid is 0.25:1.

[0046] The CAS number of the dimer fatty acid is 61788-89-4.

[0047] The infrared spectrum shows that at 3534.50cm -1 A strong absorption of -OH stretching vibration appeared at the site, indicating that the product contained a large number of hydroxyl groups.

[0048] At 2827cm -1 The characteristic peak of CH appeared at 1739.35 cm -1 A strong absorption peak appeared at the ester, and the wave number of the characteristic peak was 1725-1750cm -1 , so it can be confirmed that the product contains ester bonds.

[0049] 1300~1100cm -1 The CO characteristic peak appeared at , further verifying the existence of ester bond.

[0050] The preparation method of polyester polyol involves the following chemical reaction process:

[0051]

[0052] Preparation Example 2

[0053] The preparation method of polyether polyol comprises the following steps:

[0054] In a nitrogen environment, trihydroxyethyl isocyanurate and a double metal cyanide complex catalyst are put into a reactor; then epichlorohydrin is added into the reactor, and the reaction is carried out at 2MPa and 130°C for 2h; after the reaction is completed, unreacted epichlorohydrin is removed by heating to obtain a polyether polyol;

[0055] The feeding molar ratio of tris(hydroxyethyl)isocyanurate and epichlorohydrin is 1:1.2; and the feeding amount of the double metal cyanide complex catalyst is 0.15% of the weight of tris(hydroxyethyl)isocyanurate.

[0056] The sample was tested using a Fourier transform infrared spectrometer (FT-IR) to obtain information about the functional groups in the molecule. Results: The FT-IR spectrum of PECH shows the stretching vibration absorption peak of the hydroxyl group (OH) (about 3445 cm -1 ), the stretching vibration absorption peak of the ether bond (CO) (about 1095cm -1 ), and the stretching vibration absorption peak of the C-Cl bond (about 750cm -1 and 704cm -1). These characteristic peaks indicate that the synthesized product contains hydroxyl, ether bond and chloromethyl.

[0057] The preparation method of polyether polyol involves the following chemical reaction process:

[0058]

[0059] Example 1

[0060] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0061] 50 parts of polyether polyol (from Preparation Example 2), 50 parts of polyester polyol (from Preparation Example 1), 0.5 parts of catalyst, 6 parts of toluene diisocyanate, 6 parts of water, and 1 part of dimethyl silicone oil; wherein the catalyst is composed of DBU and thiourea in a weight ratio of 4:1.

[0062] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0063] Take 50 parts of polyether polyol (from Preparation Example 2), 50 parts of polyester polyol (from Preparation Example 1), and 6 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat to 85°C under a nitrogen environment, and react at 85°C for 2 hours; then add 0.5 parts of catalyst, 6 parts of water, and 1 part of dimethyl silicone oil into the reactor, mix thoroughly, heat to 150°C, and react for 5 hours; after the reaction is completed, cool to room temperature to obtain a barrier and explosion suppression material.

[0064] Example 2

[0065] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0066] 80 parts of polyether polyol (from Preparation Example 2), 80 parts of polyester polyol (from Preparation Example 1), 0.8 parts of catalyst, 10 parts of toluene diisocyanate, 10 parts of water, and 2 parts of dimethyl silicone oil; wherein the catalyst is composed of DBU and thiourea in a weight ratio of 4:1.

[0067] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0068] Take 80 parts of polyether polyol (from Preparation Example 2), 80 parts of polyester polyol (from Preparation Example 1), and 10 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat to 85°C under a nitrogen environment, and react at 85°C for 3 hours; then add 0.8 parts of catalyst, 10 parts of water, and 2 parts of dimethyl silicone oil into the reactor, mix thoroughly, heat to 155°C, and react for 6 hours; after the reaction is completed, cool to room temperature to obtain a barrier and explosion suppression material.

[0069] Example 3

[0070] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0071] 65 parts of polyether polyol (from Preparation Example 2), 65 parts of polyester polyol (from Preparation Example 1), 0.7 parts of catalyst, 8 parts of toluene diisocyanate, 8 parts of water, and 1.5 parts of dimethyl silicone oil; wherein the catalyst is composed of DBU and thiourea in a weight ratio of 4:1.

[0072] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0073] Take 65 parts of polyether polyol (from Preparation Example 2), 65 parts of polyester polyol (from Preparation Example 1), and 8 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat to 85°C under a nitrogen environment, and react at 85°C for 2.5 hours; then add 0.7 parts of catalyst, 8 parts of water, and 1.5 parts of dimethyl silicone oil into the reactor, mix thoroughly, heat to 152°C, and react for 5.5 hours; after the reaction is completed, cool to room temperature to obtain a barrier and explosion suppression material.

[0074] Example 4

[0075] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0076] 60 parts of polyether polyol (from Preparation Example 2), 60 parts of polyester polyol (from Preparation Example 1), 0.6 parts of catalyst, 7 parts of toluene diisocyanate, 7 parts of water, and 1 part of dimethyl silicone oil; wherein the catalyst is composed of DBU and thiourea in a weight ratio of 4:1.

[0077] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0078] Take 60 parts of polyether polyol (from Preparation Example 2), 60 parts of polyester polyol (from Preparation Example 1), and 7 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat to 85°C under a nitrogen environment, and react at 85°C for 2 hours; then add 0.6 parts of catalyst, 7 parts of water, and 1 part of dimethyl silicone oil into the reactor, mix thoroughly, heat to 150°C, and react for 6 hours; after the reaction is completed, cool to room temperature to obtain a barrier and explosion suppression material.

[0079] Example 5

[0080] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0081] 70 parts of polyether polyol (from Preparation Example 2), 70 parts of polyester polyol (from Preparation Example 1), 0.7 parts of catalyst, 9 parts of toluene diisocyanate, 9 parts of water, and 2 parts of dimethyl silicone oil; wherein the catalyst is composed of DBU and thiourea in a weight ratio of 4:1.

[0082] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0083] Take 70 parts of polyether polyol (from Preparation Example 2), 70 parts of polyester polyol (from Preparation Example 1), and 9 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat to 85°C under a nitrogen environment, and react at 85°C for 2.8 hours; then add 0.7 parts of catalyst, 9 parts of water, and 2 parts of dimethyl silicone oil into the reactor, mix thoroughly, heat to 155°C, and react for 5 hours; after the reaction is completed, cool to room temperature to obtain a barrier and explosion suppression material.

[0084] Comparative Example 1

[0085] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0086] 100 parts of polyether polyol (from Preparation Example 2), 0.5 parts of catalyst, 6 parts of toluene diisocyanate, 6 parts of water, and 1 part of dimethyl silicone oil; wherein the catalyst is composed of DBU and thiourea in a weight ratio of 4:1.

[0087] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0088] Take 100 parts of polyether polyol (from Preparation Example 2) and 6 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat to 85°C under a nitrogen environment, and react at 85°C for 2 hours; then add 0.5 parts of catalyst, 6 parts of water, and 1 part of dimethyl silicone oil into the reactor, mix thoroughly, heat to 150°C, and react for 5 hours; after the reaction is completed, cool to room temperature to obtain a barrier and explosion suppression material.

[0089] Comparative Example 2

[0090] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0091] 100 parts of polyester polyol (from Preparation Example 1), 0.5 parts of catalyst, 6 parts of toluene diisocyanate, 6 parts of water, and 1 part of dimethyl silicone oil; wherein the catalyst is composed of DBU and thiourea in a weight ratio of 4:1.

[0092] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0093] 100 parts of polyester polyol (from Preparation Example 1) and 6 parts of toluene diisocyanate were put into a reactor and mixed thoroughly, heated to 85°C under a nitrogen environment, and reacted at 85°C for 2 hours; then 0.5 parts of catalyst, 6 parts of water, and 1 part of dimethyl silicone oil were added to the reactor, mixed thoroughly, heated to 150°C, and reacted for 5 hours; after the reaction was completed, cooled to room temperature to obtain a barrier explosion suppression material.

[0094] Comparative Example 3

[0095] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0096] 50 parts of polyether polyol (from Preparation Example 2), 50 parts of polyester polyol (from Preparation Example 1), 0.5 parts of catalyst, 6 parts of toluene diisocyanate, 6 parts of water, and 1 part of dimethyl silicone oil; wherein the catalyst is DBU.

[0097] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0098] Take 50 parts of polyether polyol (from Preparation Example 2), 50 parts of polyester polyol (from Preparation Example 1), and 6 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat to 85°C under a nitrogen environment, and react at 85°C for 2 hours; then add 0.5 parts of catalyst, 6 parts of water, and 1 part of dimethyl silicone oil into the reactor, mix thoroughly, heat to 150°C, and react for 5 hours; after the reaction is completed, cool to room temperature to obtain a barrier and explosion suppression material.

[0099] Comparative Example 4

[0100] The polyurethane barrier explosion suppression material comprises the following raw materials in parts by weight:

[0101] 50 parts of polyether polyol (from Preparation Example 2), 50 parts of polyester polyol (from Preparation Example 1), 0.5 parts of catalyst, 6 parts of toluene diisocyanate, 6 parts of water, and 1 part of dimethyl silicone oil; wherein the catalyst is thiourea.

[0102] The preparation method of polyurethane barrier explosion suppression material comprises the following steps:

[0103] Take 50 parts of polyether polyol (from Preparation Example 2), 50 parts of polyester polyol (from Preparation Example 1), and 6 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat to 85°C under a nitrogen environment, and react at 85°C for 2 hours; then add 0.5 parts of catalyst, 6 parts of water, and 1 part of dimethyl silicone oil into the reactor, mix thoroughly, heat to 150°C, and react for 5 hours; after the reaction is completed, cool to room temperature to obtain a barrier and explosion suppression material.

[0104] The barrier explosion suppression materials prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to the following performance tests, and the results are summarized in Table 1:

[0105] 1. Fuel resistance test

[0106] The sample to be tested was immersed in RP-3 fuel at 70℃±3℃, and taken out after 12 weeks to test the tensile strength loss rate in dry state. The tensile strength loss rate is: (tensile strength before immersion - tensile strength after immersion) / tensile strength before immersion * 100%.

[0107] 2. Hydrolysis resistance test

[0108] The sample to be tested is immersed in distilled water at 70℃±3℃ for 12 weeks, and after 12 weeks, the sample is taken out to test the tensile strength loss rate in the dry state. The tensile strength loss rate is: (tensile strength before immersion - tensile strength after immersion) / tensile strength before immersion * 100%.

[0109] 3. Flame retardant testing

[0110] Vertical combustion is tested according to GB / T8333-2008 Test method for combustion performance of rigid foam plastics - vertical combustion method. The sample size is 50mm×50mm×10mm.

[0111] Among them: V-0: The flame is extinguished for no more than 10 seconds; after each combustion, the dripping material does not ignite the absorbent cotton underneath; in 10 tests, no more than 5 times the flame is extinguished for more than 10 seconds.

[0112] V-1: The flame is extinguished for no more than 30 seconds. After each combustion, the dripping material does not ignite the absorbent cotton underneath. In 10 tests, no more than 5 times the flame is extinguished for more than 30 seconds.

[0113] V-2: The flame is extinguished for no more than 30 seconds; dripping is allowed to ignite the absorbent cotton below; in 10 tests, no more than 5 times the flame is extinguished for more than 30 seconds.

[0114] 4. Explosion suppression performance

[0115] Under the conditions that the initial pressure (gauge pressure) in the test container is not more than 8kPa and the single-sided ignition space is 20%, the explosion pressurization test is carried out to detect the pressurization pressure, which is required not to exceed 64kPa.

[0116] Table 1

[0117]

[0118] From Table 1, we can see that:

[0119] The polyurethane barrier explosion suppression material films of Examples 1 to 5 have the following excellent properties:

[0120] High fuel resistance: After immersion in fuel for 12 weeks, the tensile strength loss rate was less than 1.3%, showing good fuel resistance.

[0121] High hydrolysis resistance: After immersion in distilled water for 12 weeks, the tensile strength loss rate was less than 1.3%, showing good hydrolysis resistance.

[0122] Excellent flame retardancy: All samples achieved the highest flame retardancy grade V-0, indicating that they have excellent flame retardant properties.

[0123] Example 1 and Comparative Examples 1-4 illustrate:

[0124] 1. Fuel resistance

[0125] Example 1: The tensile strength loss rate is 0.9%;

[0126] Comparative Example 1: The tensile strength loss rate was 1.1%;

[0127] Comparative Example 2: The tensile strength loss rate was 30.6%;

[0128] Comparative Example 3: The tensile strength loss rate was 4.6%.

[0129] It can be seen that in Example 1, polyether polyol and polyester polyol are used at the same time, and its fuel resistance is significantly better than that of Comparative Example 2 using only polyester polyol (30.6% vs. 0.9%), and is similar to that of Comparative Example 1 using only polyether polyol (1.1% vs. 0.9%). This shows that polyether polyol plays an important role in improving fuel resistance. Example 1 using DBU and thiourea composite catalyst is better in fuel resistance than Comparative Example 3 using only DBU (4.6% vs. 0.9%) and Comparative Example 4 using only thiourea (7.8% vs. 0.9%). This shows that the composite catalyst has a synergistic effect in improving fuel resistance.

[0130] 2. Hydrolysis resistance

[0131] Example 1: The tensile strength loss rate is 1.2%;

[0132] Comparative Example 1: The tensile strength loss rate was 20.7%;

[0133] Comparative Example 2: The tensile strength loss rate was 2.8%;

[0134] Comparative Example 3: The tensile strength loss rate was 3.5%;

[0135] Comparative Example 4: The tensile strength loss rate was 5.5%;

[0136] It is explained that in Example 1, polyether polyol and polyester polyol are used at the same time, and its hydrolysis resistance is significantly better than that of Comparative Example 1 using only polyether polyol (20.7% vs. 1.2%), and is similar to that of Comparative Example 2 using only polyester polyol (2.8% vs. 1.2%). This shows that polyester polyol plays an important role in improving hydrolysis resistance. Example 1 using DBU and thiourea composite catalyst is better than Comparative Example 3 using only DBU (3.5% vs. 1.2%) and Comparative Example 4 using only thiourea (5.5% vs. 1.2%) in hydrolysis resistance. This shows that the composite catalyst has a synergistic effect in improving hydrolysis resistance.

[0137] 3. Flame retardant properties

[0138] Embodiment 1: Flame retardant grade is V-0;

[0139] Comparative Example 1: Flame retardant grade is V-0;

[0140] Comparative Example 2: Flame retardant grade is V-2;

[0141] Comparative Example 3: Flame retardant grade is V-1;

[0142] Comparative Example 4: Flame retardant grade is V-1(;

[0143] It is shown that in Example 1, polyether polyol and polyester polyol are used at the same time, and its flame retardant performance is significantly better than that of Comparative Example 2 (V-2 vs. V-0) using only polyester polyol, and is similar to that of Comparative Example 1 (V-0 vs. V-0) using only polyether polyol. This shows that polyether polyol plays an important role in improving flame retardant performance. Example 1 using DBU and thiourea composite catalyst is better than Comparative Example 3 (V-1 vs. V-0) using only DBU and Comparative Example 4 (V-1 vs. V-0) using only thiourea in flame retardant performance. This shows that the composite catalyst has a synergistic effect in improving flame retardant performance.

[0144] 4. Explosion suppression performance

[0145] Example 1: The explosion suppression pressure is 43 kPa;

[0146] Comparative Example 1: explosion suppression pressure is 60 kPa;

[0147] Comparative Example 2: The explosion suppression pressure is 47 kPa;

[0148] Comparative Example 3: explosion suppression pressure is 61 kPa;

[0149] Comparative Example 4: explosion suppression pressure is 82 kPa;

[0150] It shows that in Example 1, polyether polyol and polyester polyol are used at the same time, and its explosion suppression performance is significantly better than that of Comparative Example 1 (60kPa vs.43kPa) using only polyether polyol and Comparative Example 2 (47kPa vs.43kPa) using only polyester polyol. This shows that polyether polyol and polyester polyol have a synergistic effect in improving explosion suppression performance. Example 1 using DBU and thiourea composite catalyst is better than Comparative Example 3 (61kPa vs.43kPa) using only DBU and Comparative Example 4 (82kPa vs.43kPa) using only thiourea in explosion suppression performance. This shows that the composite catalyst has a synergistic effect in improving explosion suppression performance.

[0151] In summary, polyether polyols and polyester polyols have a synergistic effect in improving explosion suppression performance; the composite catalyst (DBU and thiourea) has a significant synergistic effect in improving fuel resistance, hydrolysis resistance, flame retardancy and explosion suppression performance, which is better than using DBU or thiourea alone.

[0152] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. Polyurethane barrier explosion suppression material, characterized in that: The invention comprises the following raw materials in parts by weight: 50-80 parts of polyether polyol, 50-80 parts of polyester polyol, 0.5-0.8 parts of catalyst, 6-10 parts of toluene diisocyanate, 6-10 parts of foaming agent, and 1-2 parts of stabilizer.

2. The polyurethane barrier explosion suppression material according to claim 1, characterized in that: The preparation method of the polyester polyol comprises the following steps: Under nitrogen protection, dimer fatty acid, adipic acid and neopentyl glycol are put into a reactor and fully mixed; the reactor is heated, the heating rate is controlled, the generated water is gradually evaporated, and the temperature of the distillation column head on the reactor is controlled to be 95-100°C; When the temperature in the reactor rises to 160-170°C, keep it at 160-170°C for 1-2 hours, then slowly raise the temperature to 200°C, remove the fractionation column when water stops coming out of the fractionation column head, continue the reaction until the acid value drops below 30, then cool it; add dibutyltin dilaurate, continue to heat to 220°C and keep it for reaction until the acid value drops below 1, then stop the reaction to obtain polyester polyol; The total molar ratio of the dimerized fatty acid and adipic acid to the molar ratio of the neopentyl glycol is 1.24:1; the molar ratio of the dimerized fatty acid to adipic acid is 0.25:

1.

3. The polyurethane barrier explosion suppression material according to claim 2, characterized in that: The CAS number of the dimer fatty acid is 61788-89-4.

4. The polyurethane barrier explosion suppression material according to claim 1, characterized in that: The preparation method of the polyether polyol comprises the following steps: In a nitrogen environment, trihydroxyethyl isocyanurate and a double metal cyanide complex catalyst are put into a reactor; then epichlorohydrin is added into the reactor, and the reaction is carried out at 1-2MPa and 130-140°C for 2-3h; after the reaction is completed, the unreacted epichlorohydrin is removed to obtain a polyether polyol.

5. The polyurethane barrier explosion suppression material according to claim 4, characterized in that: The molar ratio of trishydroxyethyl isocyanurate to epichlorohydrin is 1:1.

2.

6. The polyurethane barrier explosion suppression material according to claim 4, characterized in that: The feeding amount of the double metal cyanide complex catalyst is 0.1-0.15% of the weight of trishydroxyethyl isocyanurate.

7. The polyurethane barrier explosion suppression material according to claim 1, characterized in that: The catalyst is composed of DBU and thiourea in a weight ratio of 4:

1.

8. The polyurethane barrier explosion suppression material according to claim 1, characterized in that: The foaming agent is water.

9. The method for preparing the polyurethane barrier explosion suppression material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Preparation of polyester polyols Under nitrogen protection, dimer fatty acid, adipic acid and neopentyl glycol are put into a reactor and fully mixed; the reactor is heated, the heating rate is controlled, the generated water is gradually evaporated, and the temperature of the distillation column head on the reactor is controlled to be 95-100°C; When the temperature in the reactor rises to 160-170°C, keep it at 160-170°C for 1-2 hours, then slowly raise the temperature to 200°C, remove the fractionation column when water stops coming out of the fractionation column head, continue the reaction until the acid value drops below 30, then cool it; add dibutyltin dilaurate, continue to heat to 220°C and keep it for reaction until the acid value drops below 1, then stop the reaction to obtain polyester polyol; S2. Preparation of polyether polyols In a nitrogen environment, trihydroxyethyl isocyanurate and a double metal cyanide complex catalyst are put into a reactor; then epichlorohydrin is added into the reactor, and the reaction is carried out at 1-2MPa and 130-140°C for 2-3h; after the reaction is completed, the unreacted epichlorohydrin is removed to obtain a polyether polyol. S3. Mixing and foaming Take 50-80 parts of polyether polyol, 50-80 parts of polyester polyol and 6-10 parts of toluene diisocyanate, put them into a reactor for thorough mixing, heat up to 85°C under a nitrogen environment, and react at 85°C for 2-3 hours; then add 0.5-0.8 parts of catalyst, 6-10 parts of foaming agent and 1-2 parts of stabilizer into the reactor, mix thoroughly, heat up to 150-155°C, and react for 5-6 hours; after the reaction is completed, cool to room temperature to obtain a barrier explosion suppression material.

10. Application of polyurethane barrier explosion suppression material, characterized in that: The polyurethane barrier explosion suppression material according to any one of claims 1 to 8 or the polyurethane barrier explosion suppression material prepared by the preparation method according to claim 9 is used as a filling material in a fuel tank.

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