Polyaniline-graphene-carbon nitride hybrid modified blast-resistant elastomeric coating material

Abstract

The application provides a polyaniline graphene carbon nitride hybrid modified anti-explosion elastomer coating material, relates to the technical field of flame-retardant anti-explosion composite materials, and comprises an isocyanate prepolymer as component A, polyether polyol and an amine-based chain extender as component B, secondary doped polyaniline graphene and ammonium polyphosphate (APP) as flame retardants added into the A and B components respectively to obtain a secondary doped polyaniline graphene carbon nitride hybrid material modified anti-explosion elastomer coating material. The secondary doped polyaniline graphene carbon nitride hybrid material modified anti-explosion elastomer coating material disclosed by the application adopts layered secondary doped polyaniline graphene carbon nitride material for secondary doping, so that the ammonium polyphosphate is not prone to agglomeration, the flame-retardant anti-explosion effect of the material is improved, energy is saved efficiently, the cost is reduced, and the material is conducive to industrialized wide popularization and application.

Description

[0001] The present application claims priority to the Chinese patent application No. 202211740536.8, filed on December 30, 2022, and entitled "A secondary doped state graphene modified anti-blast elastomer coating material", the whole content of which is incorporated herein by reference. TECHNICAL FIELD

[0002] The present application relates to the technical field of anti-blast elastomer composite materials, and particularly relates to a polyaniline graphene carbon nitride hybrid modified anti-blast elastomer coating material. BACKGROUND

[0003] The polyurea anti-blast elastomer coating material is widely used due to its good flexibility, high strength, fast curing speed, insensitivity to environmental temperature and humidity, and thick coating after one construction. However, the coating material is composed of a semi-prepolymer generated by the reaction of isocyanate and hydroxyl-terminated polyether, and amino-terminated polyether and amine curing agent. As a high molecular material, it is easy to catch fire and burn, and emit a large amount of toxic gas. Therefore, it is particularly important to develop a flame-retardant anti-blast elastomer coating material.

[0004] The existing technology mainly includes organic phosphorus flame retardants and inorganic phosphorus flame retardants. In the application of ammonium polyphosphate (APP) as a phosphorus flame retardant, there are still defects: first, the use of ammonium polyphosphate (APP) alone has low flame retardant efficiency: in the prior art, only when the addition amount reaches a certain amount, ammonium polyphosphate (APP) can give the polymer the necessary flame retardant safety. Second, when ammonium polyphosphate (APP) plays a flame-retardant role in the gas phase, it releases •PO free radicals to interrupt the combustion chain reaction, which makes it generate more smoke and toxic gases in the actual use process. Third, the main condensed phase flame-retardant mechanism of ammonium polyphosphate (APP) is to promote the formation of a porous carbon layer in the polymer, however, studies have shown that the addition of ammonium polyphosphate (APP) can improve the flowability of the polymer in the molten state, thus making the carbon layer formed has low strength and is not resistant to ablation. Fourth, as a polar material, ammonium polyphosphate (APP) has poor compatibility with polymers, and its introduction into the composite material can reduce the mechanical properties of the polymer composite material while flame-retardant, affecting the practicability.

[0005] In the prior art, methods for compensating for the above defects of ammonium polyphosphate (APP) can be generally divided into two types according to operation means, one is surface modification treatment of ammonium polyphosphate (APP), and the other is the use of ammonium polyphosphate (APP) together with a synergist. However, there are still many defects, and the surface modified ammonium polyphosphate (APP) has problems such as complex process and high cost, and has a long time cycle from design to production, which is not conducive to market application and promotion. The method of using ammonium polyphosphate (APP) together with a synergist has defects such as easy agglomeration of carbon nitride material in the use process, which greatly reduces the flame retardant effect of ammonium polyphosphate. SUMMARY

[0006] The application provides an anti-explosive elastomer coating material containing secondary doped polyaniline, and adopts layered nanocarbon material to modify secondary doped polyaniline and ammonium polyphosphate to realize synergistic effect and improve the flame retardant effect of ammonium polyphosphate in the anti-explosive elastomer coating material.

[0007] The application provides an anti-explosive elastomer coating material modified by polyaniline graphene carbon nitride hybrid, which comprises A component and B component, wherein an isocyanate semi-prepolymer is used as the A component, polyether polyol and an amine-based chain extender are used as the B component, secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate are used as flame retardants and added into the A component and the B component, and thus the anti-explosive elastomer coating material modified by the secondary doped polyaniline graphene carbon nitride hybrid material is obtained.

[0008] Optionally, when the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate are added into the A component as flame retardants, the mass percentage of the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate as the flame retardants in the A component is 2%-8%.

[0009] Optionally, when the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate are added into the B component as flame retardants, the mass percentage of the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate as the flame retardants in the B component is 6%-10%.

[0010] Optionally, in the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate, the mass percentage of the ammonium polyphosphate is 10%-15%.

[0011] Optionally, the A component comprises raw materials with the following mass percentages: 89.4% of the mass percentage of the isocyanate semi-prepolymer and 10.6% of the mass percentage of the flame retardant; the B component comprises raw materials with the following mass percentages: 36.6% of the mass percentage of T-5000, 28% of the mass percentage of D-2000, 20% of the mass percentage of E-100 and 15.4% of the mass percentage of the flame retardant; and the isocyanate index is 1.08.

[0012] Optionally, the preparation method of the A component is as follows:

[0013] The flame retardant is added to the hydroxyl-terminated polyether, wherein the flame retardant includes the second doped polyaniline graphene-C3N4 hybrid material and ammonium polyphosphate, and heating is performed to 90 DEG C, vacuum stirring is performed for 1-2 h, moisture present is removed, and cooling is performed to a certain temperature under nitrogen protection, then the isocyanate mixture is added to the reaction kettle, the temperature is raised to (80±4) DEG C and maintained for 2 h to ensure complete reaction. The entire reaction requires being performed under nitrogen protection, and the generated prepolymer must also be flushed with nitrogen for sealing.

[0014] Optionally, the preparation method of the B component is as follows:

[0015] The pigment, filler, flame retardant, auxiliary agent and appropriate hydroxyl-terminated polyether are mixed, wherein the flame retardant includes the second doped polyaniline graphene-C3N4 hybrid material and ammonium polyphosphate, grinding is performed on a three-roll mill, after a certain fineness requirement is reached, the ground slurry is poured into the reaction kettle, the hydroxyl-terminated polyether and the chain extender are added, uniform mixing is performed, and then the material is filtered with a 200-mesh screen during the discharging process.

[0016] Optionally, the preparation method of the polyaniline graphene-C3N4 hybrid modified anti-blast elastomer coating material includes the following steps:

[0017] Step 1, the hydroxyl-terminated polyether of the A component is added to a stirrer, and vacuum heating dehydration is performed until the moisture content is less than 0.5 ‰;

[0018] Step 2, the flame retardant is added to the dehydrated hydroxyl-terminated polyether obtained in step 1 under temperature and time control, wherein the flame retardant includes the second doped polyaniline graphene-C3N4 hybrid material and ammonium polyphosphate, then the isocyanate mixture is added, and the reaction mixture is reacted under stepwise temperature rising and stepwise temperature control and holding;

[0019] Step 3, after the reaction is completed, temperature control and cooling are performed, 100-mesh copper mesh filtration is performed, and nitrogen protection is performed to obtain the A component;

[0020] Step 4, the material of the B component is added to the reaction kettle, and vacuum heating dehydration is performed until the moisture content is less than 0.5 ‰;

[0021] Step 5, the ground pigment and filler are added to the reaction kettle in step 4, and high-speed stirring is performed, then vacuum heating degassing is performed;

[0022] Step 6, after the mixture in step 5 is cooled to <60 DEG C, 100-mesh copper mesh filtration is performed, the filtrate is filled, and nitrogen protection is performed to obtain the B component.

[0023] The present application has the following beneficial technical effects:

[0024] The application provides a polyaniline graphene carbon nitride hybrid modified anti-explosion elastomer coating material, which can be conveniently sprayed on the surface of various materials and greatly improves the flame-retardant anti-explosion effect of the object; is conducive to industrialization promotion and cost reduction; the layered secondary doped polyaniline graphene carbon nitride material is used for modification, effectively solves the problem that the nitrogen-containing carbon material is prone to agglomeration when the ammonium polyphosphate (APP) flame-retardant material is used in conjunction with an auxiliary agent, greatly improves the flame-retardant performance while maintaining the original mechanical strength; the layered secondary doped polyaniline graphene carbon nitride material is used for modification of the A component and the B component, effectively avoids the generation of a large amount of smoke and toxic gas in actual use; is conducive to environmental protection and green application, and is conducive to wide application;

[0025] To sum up, the application discloses an anti-explosion elastomer coating material modified by polyaniline graphene carbon nitride hybrid, the layered secondary doped polyaniline graphene carbon nitride material is used for modification of the A component and the B component, so that the ammonium polyphosphate APP in the anti-explosion elastomer coating material does not agglomerate, and the flame-retardant anti-explosion effect of the material is improved; no smoke and toxic gas is generated in actual use, which is conducive to efficient energy saving, cost reduction, environmental protection, and wide industrial application. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiment description. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative effort.

[0027] Figure 1 It is an electron microscope scanning graph of the anti-explosion elastomer coating material containing polyaniline.

[0028] Figure 2 It is an electron microscope scanning graph of the anti-explosion elastomer coating material containing polyaniline. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solutions and advantages of the present application more clear, the following will further describe the present application with reference to the drawings. Obviously, the described embodiments are only some of the embodiments of the present application, but not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present application.

[0030] In view of the above defects of the prior art, the technical problems to be solved by the embodiments of the present application are that the ammonium polyphosphate (APP) flame-retardant material in the prior art has the defects that carbon nitride material is easy to agglomerate when a synergist is used, resulting in poor flame-retardant effect, and that the ammonium polyphosphate (APP) flame-retardant material is easy to generate a large amount of smoke and toxic gas in actual use, which is not conducive to environmental protection.

[0031] Based on this, the present application provides a polyaniline graphene carbon nitride hybrid modified anti-blast elastomer coating material, which comprises A component and B component, wherein the isocyanate semi-prepolymer is the A component, the polyether polyol and the amine-based chain extender are the B component, the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate are added as flame retardants to the A component and the B component, and the secondary doped polyaniline graphene carbon nitride hybrid material modified anti-blast elastomer coating material is obtained.

[0032] Optionally, when the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate are added as flame retardants to the A component, the mass percentage content of the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate as flame retardants in the A component is 2%-8%.

[0033] Optionally, when the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate are added as flame retardants to the B component, the mass percentage content of the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate as flame retardants in the B component is 6%-10%.

[0034] Optionally, in the secondary doped polyaniline graphene carbon nitride hybrid material and the ammonium polyphosphate, the mass percentage of the ammonium polyphosphate is 10%-15%.

[0035] Optionally, the A component comprises raw materials in the following mass percentages: the mass percentage of the isocyanate semi-prepolymer is 89.4%, and the mass percentage of the flame retardant is 10.6%; the B component comprises raw materials in the following mass percentages: the mass percentage of T-5000 is 36.6%, the mass percentage of D-2000 is 28%, the mass percentage of E-100 is 20%, and the mass percentage of the flame retardant is 15.4%; and the isocyanate index is 1.08.

[0036] Optionally, the preparation method of the A component is as follows:

[0037] The end hydroxyl polyether is added with a flame retardant, wherein the flame retardant includes a second doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate, heated to 90℃, vacuum stirring for 1~2h, removing the existing moisture, and cooled to a certain temperature under nitrogen protection, then an isocyanate mixture is added into the reaction kettle, the temperature is raised to (80±4)℃ and kept for 2h to ensure the reaction is complete. The whole reaction requires to be carried out under nitrogen protection, and the generated prepolymer must also be flushed into nitrogen for sealing.

[0038] Optionally, the preparation method of the B component is:

[0039] The pigments, fillers, flame retardants, additives and appropriate end amino polyether are mixed, wherein the flame retardant includes a second doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate, and are ground on a three-roll mill. After reaching a certain fineness requirement, the ground slurry is put into a reaction kettle, end amino polyether and chain extender are added, and after mixing uniformly, the material is discharged and filtered with a 200 mesh screen during the discharging process.

[0040] Optionally, the preparation method of the polyaniline graphene carbon nitride hybrid modified anti-blast elastomer coating material includes the following steps:

[0041] Step 1, the end hydroxyl polyether of the A component is added into a stirrer, and vacuum heating dehydration is carried out until the moisture content is less than 0.5‰;

[0042] Step 2, the flame retardant is added into the dehydrated end hydroxyl polyether obtained in step 1 under temperature and time control, wherein the flame retardant includes a second doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate, and then an isocyanate mixture is added. The reaction mixture is reacted under stepwise temperature rising and stepwise temperature control and holding;

[0043] Step 3, after the reaction is completed, the temperature is controlled and cooled, filtered with a 100 mesh copper screen, and stored under nitrogen protection to obtain the A component;

[0044] Step 4, the material of the B component is added into a reaction kettle, and vacuum heating dehydration is carried out until the moisture content is less than 0.5‰;

[0045] Step 5, the ground pigments and fillers are added into the reaction kettle of step 4, and high-speed stirring is carried out; then vacuum heating degassing is carried out;

[0046] Step 6, after the mixture in step 5 is cooled to <60℃, it is filtered with a 100 mesh copper screen, the filtrate is filled, and nitrogen protection is carried out to obtain the B component.

[0047] Further, step 1, the specific operation is: the end hydroxyl polyether of the A component is added into a stirrer, and the temperature is controlled to rise to 105℃ within 30min under stirring, the system is opened to vacuum, the vacuum degree is above 0.075MPa, and then the temperature is raised to 115℃ for dehydration.

[0048] Further, in step 2, the temperature control and time control are that the flame retardant (the second doped state of polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate (APP)) is added within 30 min before the material temperature rises to 60℃;

[0049] Further, in step 2, the stepwise temperature rise and stepwise temperature control and holding include first-order temperature rise, first-order holding, second-order temperature rise, and second-order holding; the first-order temperature rise is to rise the temperature to 75℃ within 20 min; the first-order holding is to control the temperature at 75±2℃ for 2 h; the second-order temperature rise is to rise the temperature to 82℃ within 10 min; and the second-order holding is to control the temperature at 82±2℃ for 2 h.

[0050] Further, in step 3, the temperature control cooling is to control the cooling speed to make the material temperature below 60℃ within 20 min;

[0051] Further, in step 4, the specific operation is as follows: the macromolecular terminal amino polyether and the flame retardant (the second doped state of polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate (APP)) are mixed, and then added into a stirrer for heating and stirring; then the small molecular weight terminal amino polyether and the chain extender are added; the mixture is heated and stirred to rise the temperature to 105℃ within 30 min, and then the vacuum system is opened to continue to rise the temperature to 110℃ under the vacuum degree of 0.075 MPa or above for dehydration;

[0052] Further, in step 2, the isocyanate mixture comprises at least one of 4,4,-diphenylmethane diisocyanate (MDI-100), 2,4, diphenylmethane diisocyanate, 4,4, -diphenylmethane diisocyanate, isophorone diisocyanate, 4,4,-dicyclohexylmethane diisocyanate or naphthalene diisocyanate. The hydroxyl-terminated polyether comprises at least one of PTMG1000, PTMG2000, polyester diol; wherein the PTMG1000 has a relative molecular mass of 1000±50, a hydroxyl value of 107-118 mgKOH / g; the PTMG2000 has a relative molecular mass of 2000±50, a hydroxyl value of 54.7-57.5 mgKOH / g; the polyester diol comprises at least one of polycaprolactone diol, polycarbonate diol; the macromolecular weight amino-terminated polyether has a molecular weight of 1000-8000; the small molecular weight amino-terminated polyether has a molecular weight of 100-800; the amino-terminated polyether comprises D-2000, T-5000; the chain extender is one or more of isophorone diamine, 4,4, -bis-sec-butylamino dicyclohexylmethane, 3,3, -dimethyl-4,4, -bis-sec-butylamino-dicyclohexylmethane, methyldiethanolamine, diethyltoluene diamine, dimethylthio toluene diamine, 4,4 '-methylene bis, 4,4-methylene bis or N,N'-bis-sec-amyl cyclohexane diamine; the pigment and filler comprise one or more of titanium dioxide, talc, kaolin.

[0053] Further, in step 5, the high speed rotation speed is 1000 rpm; the vacuum heating degassing is performed at a vacuum degree of 0.075 MPa, a heating temperature of 80±2℃, and a degassing time of 15 min.

[0054] The embodiment of the present application also provides a spraying method of the polyimine graphene carbon nitride hybrid modified blast-resistant elastomer coating material, which comprises spraying the mixture of the A component and the B component at a hydraulic pressure of 2000-2500 psi, a material temperature of 60-66℃, and a volume ratio of 1:1; the sprayed coating thickness is 1.5-2.0 mm. The sprayed substrate is a PVC plate, a galvanized steel plate, or a concrete plate; the polyimine graphene carbon nitride hybrid modified blast-resistant elastomer coating material of the embodiment of the present application can be widely used in the purpose of flame-retardant blast resistance.

[0055] The preparation method of the A component (prepolymer) is as follows: the hydroxyl-terminated polyether is heated to 90℃, vacuum stirring is performed for 1-2 h to remove the existing moisture, and then the isocyanate monomer is added into the reaction kettle under the protection of nitrogen, the temperature is raised to (80±4)℃ and maintained for 2 h to ensure the complete reaction. The whole reaction is required to be performed under the protection of nitrogen, and the generated prepolymer must be sealed by flushing with nitrogen.

[0056] The method for preparing the B component is: a certain amount of pigment, filler, flame retardant, auxiliary agent and appropriate amount of terminal amino polyether are mixed and ground on a three-roll mill, after reaching a certain fineness requirement, the ground slurry is put into a reaction kettle, amine-based polyether and chain extender are added, and after mixing uniformly, the material is discharged, and the material is filtered through a 100 mesh screen during the discharging process

[0057] The isocyanate prepolymer is used as the A component, the polyether polyol and amine-based chain extender are used as the B component, and the secondary doped graphene and ammonium polyphosphate (APP) are used as the flame retardant and added into the A and B components respectively, and a special spraying equipment is used to prepare the flame-retardant and explosion-resistant elastomer coating material.

[0058] In the formula, T-5000 is polyoxypropylene triamine (terminal amino polyether), D-2000 is polyether amine (terminal amino polyether), E-100 is diethyl toluene diamine (chain extender), RGO is graphene, and MDI-50 is a mixture of 2,4-diphenyl methane diisocyanate and 4,4'-diphenyl methane diisocyanate.

[0059] Example 1: Preparation of secondary doped polyaniline graphene carbon nitride hybrid material

[0060] (1) A 1 mol / L perchloric acid solution is prepared as a doping acid system, and two 20 ml portions of the perchloric acid solution are taken, one portion is added with aniline (ANI) and a certain amount of g-C3N4 nanosheet, and the other portion is added with ammonium persulfate (APS), wherein the molar ratio of aniline to ammonium persulfate is n(ANI):n(APS)=0.8:1, and the two are uniformly mixed by a magnetic stirrer for 1-2 h, and then left to stand at room temperature for 24 h, and the obtained product is washed with ethanol and deionized water to neutral, and then dried and ground to obtain a primary doped polyaniline (PANI).

[0061] (2) Graphene RGO is added to the aniline system, and the mass ratio of RGO to ANI is set to 1:5-1:25, and the above preparation steps are repeated to prepare a primary doped graphene carbon nitride hybrid material.

[0062] (3) The primary doped graphene carbon nitride hybrid material obtained in (2) is added with excess ammonia water for de-doping, and stirred by a magnetic stirrer for 1-2 h, and then left to stand at room temperature for 24 h, and the obtained product is washed with ethanol and deionized water to neutral, and then dried and ground to obtain an intrinsic state graphene polyaniline carbon nitride hybrid material.

[0063] (4) The graphene and the intrinsic state graphene polyaniline carbon nitride hybrid material are added to 1 mol / L perchloric acid solution at a ratio of 1:20, mixed and stirred, and then left to stand for 24 h, and then filtered, washed with ethanol and deionized water to neutral, and finally dried and ground to obtain a secondary doped polyaniline graphene carbon nitride hybrid material.

[0064] Example 2: Preparation of the secondary doped polyaniline graphene carbon nitride hybrid material modified blast-resistant elastomer coating material

[0065] In a specific embodiment, the secondary doped polyaniline graphene carbon nitride hybrid material modified blast-resistant elastomer coating material base formula (in mass parts):

[0066] The A component (NCO mass fraction 17%) formula is isocyanate semi-prepolymer 89.4, flame retardant 10.6;

[0067] The B component formula is T-5000 36.6, D-2000 28, E-100 20, and flame retardant 15.4;

[0068] The specific operation is as follows:

[0069] I. Preparation of A component (prepolymer):

[0070] 1. End-capped material dehydration process

[0071] (1) Check whether the reaction kettle and auxiliary devices, vacuum system are normal;

[0072] (2) Measure and weigh 36 g of hydroxyl-terminated polyether PTMG1000 and add it to the reaction kettle for dehydration process operation;

[0073] (3) Turn on the stirrer (gradually adjust to medium speed, 600 rpm) and the heating device, control the temperature to rise to 105°C within 30 min, open the vacuum system, continue to heat to 110°C, maintain the temperature at 115±3°C, keep the vacuum degree above 0.075 MPa, and vacuum dehydration for more than 2 h;

[0074] (4) Close the vacuum system and open the exhaust valve, fill nitrogen to restore to normal pressure, take a sample to measure the moisture content, if the moisture content is still higher than 0.5‰, repeat the operation of (3) until the moisture content of the polyether is less than 0.5‰;

[0075] (5) After the moisture content is qualified, close the vacuum system and open the exhaust valve, fill nitrogen to restore to normal pressure, cool to a temperature <60°C for use.

[0076] 2. Preparation of semi-prepolymer

[0077] (1) Turn on the stirrer and heating device, add 4 g of dehydrated hydroxyl-terminated polyether PTMG650, 2 g of secondary doped graphene, 0.3 g of ammonium polyphosphate (APP), and 60 g of isocyanate MDI-50; control the feeding speed, which must be slowly and uniformly completed within 30 min, and the feeding should be completed before the material temperature rises to 60°C;

[0078] (2) After the completion of feeding, the temperature is raised to 75°C within 20 minutes, and the temperature is controlled at 75±2°C for 2 hours of reaction preservation; then the temperature is raised to 82°C within 10 minutes, and the temperature is controlled at 82±2°C for 2 hours of reaction preservation, and the material temperature is strictly controlled not to exceed 86°C;

[0079] (3) After the completion of reaction, the heating is stopped, and the cooling device is started to control the cooling speed to make the material temperature drop to below 60°C within 20 minutes, and the stirring is continued for 30 minutes;

[0080] (4) After filtration with a 100-mesh copper screen, it is filled and packaged, and the nitrogen gas protection in the packaging barrel after filling is completed is necessary to ensure the sealing of the packaging container, and the A component is obtained. At the same time, the NCO index of the semi-prepolymer is determined by sampling.

[0081] After detection, the isocyanate index is 1.08;

[0082] II. Preparation of B component:

[0083] (1) Check whether the reaction kettle and each accessory device are operating normally;

[0084] (2) Measure the materials and add them to the reaction kettle for dehydration process operation:

[0085] First, 60g of macromolecular weight (molecular weight 1000-8000) amino-terminated polyether (T-5000) is mixed with 15g of flame retardant (including 13g of secondary doped graphene and 2g of ammonium polyphosphate (APP)), the stirrer (gradually adjusted to medium speed, 600rpm) and the heating device are started, then 22g of chain extender E-100 and D-2000 with small molecular weight (molecular weight 100-800) are added; control the temperature to rise to 105°C within 30 minutes, then open the vacuum system and continue to heat to 110°C, keep the temperature at 110±3°C, keep the vacuum degree above 0.075MPa, and dehydrate for more than 2 hours;

[0086] (3) Close the vacuum system and open the exhaust valve, fill nitrogen gas to restore to normal pressure, and measure the moisture content after sampling. If the moisture content is still higher than 0.5‰, repeat the operation of (2) until the moisture content is less than 0.5‰;

[0087] (4) After the moisture content is qualified, close the vacuum system and open the exhaust valve, and fill nitrogen gas to restore to normal pressure.

[0088] (5) Measure 1.8g of pigment titanium dioxide and 1.2g of filler kaolin after grinding and add them to the reaction kettle, and stir at high speed (1000rpm) for 1 hour;

[0089] (6) Start the vacuum system and keep the vacuum degree at 0.075MPa, and deaerate for 15 minutes at 80±2°C;

[0090] (7) Turn off the vacuum system and heating device, low speed stirring, recharging nitrogen to vacuum, cooling to the material temperature < 60 ℃ after 100 mesh copper screen filter filling, filling complete package barrel must be filled with nitrogen protection, to ensure the sealing of the packaging container, get B component.

[0091] In the preparation of A component, the reaction process is strictly controlled by stepwise heating and stepwise temperature holding; the isocyanate in A component is prevented from accelerating self-polymerization due to excessive temperature, and the reaction is prevented from consuming too much NCO, so as to effectively maintain the NCO content in the system and ensure the product performance; at the same time, the reaction process is strictly controlled by stepwise heating and stepwise temperature holding, which effectively prevents the reaction from being unable to reach the reaction endpoint for a long time due to excessive temperature, avoids a large amount of unreacted hydroxyl and NCO in the system, and effectively ensures the flame retardance and explosion resistance;

[0092] In the preparation of B component, the process operation of first mixing the high molecular weight amino polyether with the flame retardant and then adding the low molecular weight amino polyether is adopted, which effectively avoids the problem of reduced amine value caused by volatilization loss of low molecular weight amino polyether, greatly increases the stability of the system, and improves the performance of the product;

[0093] Example 3: Spray sample preparation

[0094] The secondary doped polyaniline graphene carbon nitride hybrid material modified anti-explosion elastomer coating material obtained in the above example 2 is applied, and the spraying equipment is H-xp3 main machine and Fusion-AP spray gun produced by American Graco company. The main process parameters are: hydraulic pressure 2000-2500 psi, material temperature 60-66 ℃, and the volume ratio of A component and B component is 1:1. The spraying substrate is PVC plate, and the coating thickness is 1.5-2.0 mm. The sprayed sample is cured at 50 ℃ for 2 days and is ready for use.

[0095] Test example 4

[0096] In the preparation of A component and the preparation of B component in example 2, the secondary doped polyaniline graphene carbon nitride hybrid material is replaced by the primary doped graphene carbon nitride hybrid material obtained in (2) of example 1 to obtain a primary doped polyaniline graphene carbon nitride hybrid material modified anti-explosion elastomer coating material.

[0097] The secondary doped polyaniline graphene carbon nitride hybrid material modified anti-explosion elastomer coating material obtained in the above test example and the secondary doped polyaniline graphene carbon nitride hybrid material modified anti-explosion elastomer coating material obtained in example 2 are both scanned by electron microscope; and the observation results are compared as follows:

[0098] As Figure 1As shown, the primary doped state polyaniline graphene carbon nitride hybrid material modified anti-explosion elastomer coating material has a small amount of polyaniline attached to the surface of graphene, and the fiber length is relatively short, and the agglomeration is formed; Figure 2 As shown, the secondary doped state polyaniline graphene carbon nitride hybrid material modified anti-explosion elastomer coating material has a small amount of polyaniline attached to the surface of graphene, and the fiber length is relatively short, and the agglomeration is formed;

[0099] Test Example 5

[0100] The sample piece of the anti-explosion elastomer coating material of the secondary doped state polyaniline graphene carbon nitride hybrid material modified in Example 2 of the present application is sprayed on the sample piece of Example 3; and the sample piece of the anti-explosion elastomer coating material of the primary doped state polyaniline graphene carbon nitride hybrid material modified in Test Example 4 is sprayed on the sample piece of Example 3;

[0101] At the same time, they are placed in the same flame combustion environment and explosion environment for testing, and the observation and recording results are as follows:

[0102] In the above flame combustion and explosion environment, the sample piece of the anti-explosion elastomer coating material of the primary doped state polyaniline graphene carbon nitride hybrid material modified in Test Example 4 is sprayed on the sample piece of Example 3, and the sample piece appears to be burning at 15 minutes, the flame tip height is greater than 150 mm, and internal combustion droplets appear, and the sample piece is completely burned at 10 minutes;

[0103] The sample piece of the anti-explosion elastomer coating material of the secondary doped state polyaniline graphene carbon nitride hybrid material modified in Example 2 of the present application is sprayed on the sample piece of Example 3, and the sample piece does not appear to be burning within 60 minutes, and does not release a large amount of smoke and toxic gas;

[0104] It is shown that, compared with the sample piece of the anti-explosion elastomer coating material of the primary doped state polyaniline graphene carbon nitride hybrid material, the sample piece of the anti-explosion elastomer coating material of the secondary doped state polyaniline graphene carbon nitride hybrid material of the present application has a significant flame-retardant and explosion-resistant effect. Example 6

[0105] The sample piece of the anti-explosion elastomer coating of the secondary doped state polyaniline graphene carbon nitride hybrid material modified in Example 2 of the present application is sprayed on the sample piece of Example 3; and the sample piece of the coating without adding the secondary doped state polyaniline graphene carbon nitride hybrid material is sprayed; the related mechanical property detection is carried out according to GB / T 528-2009 “Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber”, GB / T 529-2008 “Determination of Tear Strength of Vulcanized Rubber or Thermoplastic Rubber (Pant, Right Angle and Crescent Shape Samples)”, and the results are as follows:

[0106] The tensile strength of the explosion-proof elastomer coating sample sprayed with no secondary doping of polyaniline graphene carbon nitride hybrid material was 23.81 MPa, the tear strength was 120.3 N / mm, and the elongation at break was 210.5%.

[0107] The sample of Example 3 sprayed with the explosion-proof elastomer coating material modified with the secondary doped polyaniline graphene carbon nitride hybrid material of Example 2 of the present invention had a tensile strength of 23.84 MPa, a tear strength of 120.5 N / mm, and an elongation at break of 211.1%.

[0108] The results show that compared with the anti-explosion elastomer coating sample without adding the secondary doped polyaniline graphene carbon nitride hybrid material, the anti-explosion elastomer coating sample of the secondary doped polyaniline graphene carbon nitride hybrid material of the present invention has no reduction in tensile strength, tear strength, and elongation at break, and still maintains the mechanical strength of the original material;

[0109] The present invention solves the problem in the existing technology that ammonium polyphosphate (APP) as a polar material has poor compatibility with polymers. When APP is introduced into composite materials, it will reduce the mechanical properties of the polymer composite materials while making them flame retardant, thus affecting their practicality.

[0110] After testing and analysis, the applicant provides the following analysis: The synergistic flame retardancy mechanism of the secondary-doped polyaniline / graphene / carbon nitride hybrid and ammonium polyphosphate (APP) is explained by the following: The amino groups in the secondary-doped polyaniline / graphene / carbon nitride hybrid react with the molecular chains of the polyurea / explosion-resistant elastomer coating to produce a strong interfacial effect, reducing the surface energy of the coating. Furthermore, the secondary-doped polyaniline / graphene / carbon nitride hybrid is uniformly dispersed within the polyurea / explosion-resistant elastomer coating, forming a labyrinthine effect. The presence of ammonium polyphosphate enhances this labyrinthine effect, improving hydrophobicity while simultaneously hindering heat transfer. When the coating is exposed to flame, the ammonium polyphosphate (APP) and the secondary-doped polyaniline / graphene / carbon nitride hybrid decompose at relatively low temperatures. The ammonium polyphosphate (APP) promotes the formation of char in the polyurea / explosion-resistant elastomer coating, generating a large amount of non-flammable water vapor that causes the polyurea / explosion-resistant elastomer coating to foam and expand, forming a char layer. The amino groups in the secondary doped polyaniline graphene carbon nitride hybrid material react with the polyurea anti-explosion elastomer coating material to promote the formation of the anti-explosion elastomer coating material network, while the self-carbonization of the secondary doped polyaniline graphene carbon nitride hybrid material promotes the cross-linking and carbonization of the polyurea anti-explosion elastomer coating material, ultimately forming a dense, continuous porous protective carbon layer.

[0111] The porous expanded protective carbon layer not only insulates heat, but also forms a labyrinth effect, prolonging the path of combustible gas and toxic gas escaping to contact the flame. Thus, the secondary doped polyaniline graphene carbon nitride hybrid material and polyphosphoric acid (APP) improve the flame retardant performance of the polyurea elastomer coating material through synergistic effect, and inhibit the release of smoke and toxic gas.

[0112] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement to part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A polyaniline graphene carbon nitride hybrid modified blast resistant elastomeric coating material characterized in that, The anti-blast elastomer coating material comprises A component and B component, wherein the isocyanate semi-prepolymer is the A component, the polyether polyol and the amine-based chain extender are the B component, the secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate are added into the A component and the B component as the flame retardant to obtain the anti-blast elastomer coating material modified by the secondary doped polyaniline graphene carbon nitride hybrid material; when the secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate are added into the A component as the flame retardant, the mass percentage of the secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate as the flame retardant in the A component is 2%-8%; when the secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate are added into the B component as the flame retardant, the mass percentage of the secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate as the flame retardant in the B component is 6%-10%; the secondary doped polyaniline graphene carbon nitride hybrid material has a layered structure.

2. The knock-resistant elastomeric coating material of claim 1, wherein, In the secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate, the mass percentage of the ammonium polyphosphate is 10%-15%.

3. The knock-resistant elastomeric coating material of claim 1, wherein, The preparation method of the A component is as follows: The flame retardant, including the secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate, is added into the hydroxyl-terminated polyether, and then the mixture is heated to 90℃, vacuum stirred for 1-2h to remove the existing moisture, cooled to a certain temperature under nitrogen protection, and then the isocyanate mixture is added into the reaction kettle, the temperature is raised to (80±4)℃ and kept for 2h to ensure the reaction is complete, the whole reaction is required to be carried out under nitrogen protection, and the generated prepolymer must also be sealed with nitrogen.

4. The knock-resistant elastomeric coating material of claim 1, wherein, The preparation method of the B component is as follows: The pigment, filler, flame retardant, auxiliary agent and appropriate amount of amino-terminated polyether are mixed, wherein the flame retardant includes the secondary doped polyaniline graphene carbon nitride hybrid material and ammonium polyphosphate, and then the mixture is ground on a three-roll mill, after reaching a certain fineness requirement, the ground slurry is put into the reaction kettle, the amino-terminated polyether and the chain extender are added, and then the mixture is uniformly mixed and discharged, and the material is filtered with a 200-mesh screen during the discharging process.

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