Electrostatically conductive blast resistant polyurea elastomer composition, electrostatically conductive blast resistant polyurea elastomer, and methods of making and using the same

Abstract

The application relates to the technical field of chemical materials, and discloses a static-conducting anti-explosion polyurea elastomer composition, a static-conducting anti-explosion polyurea elastomer and a preparation method and application thereof. The composition comprises an A component and a B component with a content weight ratio of 1:0.9-1; the A component contains the following components which are independently stored or stored in mixture of two or more: isocyanate, polyol, a first antistatic agent, diluent; the B component contains the following components which are independently stored or stored in mixture of two or more: polyether amine, chain extender, a second antistatic agent and auxiliary agent. The polyurea elastomer prepared by the application can have the static-conducting property while improving the mechanical property.

Description

Technical Field

[0001] This invention relates to the field of chemical materials technology, specifically to a conductive and explosion-proof polyurea elastomer composition, a conductive and explosion-proof polyurea elastomer, its preparation method, and its application. Background Technology

[0002] Polyurea elastomers are polymers produced by reacting polyol or amine-terminated isocyanate prepolymers or semi-prepolymers (component A) with amino compound components (component R).

[0003] Sprayed polyurea elastomer, as a high molecular polymer material, can be made to have excellent strength and elongation through molecular design. Utilizing the elasticity, high strain capacity, high ductility, strength and substrate adhesion of the polymer coating, it can be combined with substrates such as building walls. At the same time, the coating can also play a shielding role in accommodating explosive fragments.

[0004] Spray-applied polyurea explosion-proof elastomer materials can enhance the bending stiffness and resistance of walls, and absorb a lot of shock wave energy through high strain during the explosion process, thus playing an explosion-proof role.

[0005] However, like most polymer materials, sprayed polyurea materials have good insulation properties but also high surface resistivity and volume resistivity. When the polymer rubs against the external medium, the resulting static electricity is not easily released. As the static charge accumulates, it forms a static voltage. When static electricity causes corona discharge or spark discharge, if there are flammable or explosive media in the surrounding environment, it can easily cause serious accidents such as fires and explosions, which must be avoided at all costs.

[0006] Currently, polyurea is mainly used as an explosion-proof material in the petrochemical industry for the explosion-proof retrofitting of buildings, in order to improve the ability of petrochemical buildings to resist gas explosions. These applications contain a large amount of flammable and explosive media, requiring polyurea explosion-proof materials to also have good electrostatic conductivity.

[0007] To improve the electrostatic conductivity of polyurea materials, existing technologies disclose the addition of liquid antistatic agents such as quaternary ammonium salts, sulfonates, and intramium salts, or solid antistatic agents such as conductive powders to polyurea materials. However, quaternary ammonium salt antistatic agents have poor heat resistance and are prone to damaging the thermal stability of the polymer during processing, while adding a large amount of conductive powder will cause a decrease in the mechanical properties of the material and fail to meet the explosion-proof requirements.

[0008] CN111808261A discloses a conductive and explosion-proof polyurea elastomer material, which achieves excellent conductive properties of polyurea material by adding carbon nanotubes to component A. However, the conductive carbon material in this elastomer material is prone to agglomeration in the system, making it difficult to mix and disperse evenly, which affects the film formation of the polymer and leads to the problem that it is difficult to achieve both mechanical properties and conductive properties of the elastomer material. Summary of the Invention

[0009] The purpose of this invention is to overcome the shortcomings of existing polyurea elastomer materials, which have difficulty in simultaneously achieving both mechanical properties and electrostatic conductivity.

[0010] During their research, the inventors discovered that the synergistic effect of polyether antistatic agents and modified metal oxide composite polyether antistatic agents can leverage the conductivity of both while avoiding the adverse effects of physical additives on the mechanical properties of the polyurea elastomer coating. Furthermore, the aforementioned two antistatic agents exhibit good compatibility with other components in components A and B, allowing for uniform mixing and dispersion within the system without sedimentation issues. This results in a polyurea elastomer with excellent mechanical and electrostatic conductivity properties. Thus, the solution of this invention was completed.

[0011] To achieve the above objectives, the first aspect of the present invention provides a conductive and explosion-proof polyurea elastomer composition comprising component A and component B in a weight ratio of 1:0.9-1.

[0012] Component A contains the following components, which may be stored independently or in combination: isocyanate, polyol, first antistatic agent, and diluent;

[0013] The isocyanate contains at least two isocyanate groups;

[0014] The first antistatic agent is a polyether antistatic agent;

[0015] The polyol is a polyether polyol and / or a polyester polyol, and the number average molecular weight of the polyol is 200-2000.

[0016] Based on the total weight of component A, the content of isocyanate is 50-65 wt%, the content of the first antistatic agent is 8-10 wt%, the content of polyol is 25-40 wt%, and the content of diluent is 0-10 wt%.

[0017] Component B contains the following components, which may be stored independently or in combination: polyetheramine, chain extender, second antistatic agent, and additives;

[0018] The second antistatic agent is obtained by extrusion granulation after mixing the modified metal oxide with the first antistatic agent; wherein the modified metal oxide is selected from at least one of modified nano zinc oxide, modified nano tin oxide, modified nano antimony oxide, and modified silicon dioxide;

[0019] Based on the total weight of component B, the content of the polyetheramine is 35-50 wt%, the content of the chain extender is 35-50 wt%, the content of the second antistatic agent is 10-16 wt%, and the content of the auxiliary agent is 1-5 wt%.

[0020] A second aspect of the present invention provides a method for preparing a conductive and explosion-proof polyurea elastomer, the method comprising mixing the components of the composition described in the first aspect, including:

[0021] (1) The first antistatic agent is subjected to dehydration treatment I with a polyol to obtain a first mixture, and the first mixture, isocyanate, and diluent are reacted I to obtain a prepolymer; and

[0022] The polyetheramine and chain extender are subjected to dehydration treatment II to obtain a second mixture. The second mixture, the second antistatic agent and the additives are then subjected to first dispersion and ultrasonic dispersion in sequence to obtain a third mixture.

[0023] (2) Mix the prepolymer and the third mixture.

[0024] The third aspect of the present invention provides a conductive and explosion-proof polyurea elastomer prepared by the method described in the second aspect.

[0025] The fourth aspect of this invention provides the application of the electrostatically conductive and explosion-proof polyurea elastomer described in the third aspect in petrochemical equipment and buildings.

[0026] The present invention prepares a polyurea elastomer by compounding a specific amount of polyether antistatic agent with a modified metal oxide composite polyether antistatic agent, and synergistically combining polyol, polyether amine and isocyanate with a specific structure, which can improve mechanical properties while ensuring electrostatic conductivity. Detailed Implementation

[0027] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0028] In this invention, unless otherwise stated, room temperature or normal temperature refers to 25±2℃.

[0029] As previously stated, a first aspect of the present invention provides a conductive and explosion-proof polyurea elastomer composition comprising component A and component B in a weight ratio of 1:0.9-1.

[0030] Component A contains the following components, which may be stored independently or in combination: isocyanate, polyol, first antistatic agent, and diluent;

[0031] The isocyanate contains at least two isocyanate groups;

[0032] The first antistatic agent is a polyether antistatic agent;

[0033] The polyol is a polyether polyol and / or a polyester polyol, and the number average molecular weight of the polyol is 200-2000.

[0034] Based on the total weight of component A, the content of isocyanate is 50-65 wt%, the content of the first antistatic agent is 8-10 wt%, the content of polyol is 25-40 wt%, and the content of diluent is 0-10 wt%.

[0035] Component B contains the following components, which may be stored independently or in combination: polyetheramine, chain extender, second antistatic agent, and additives;

[0036] The second antistatic agent is obtained by extrusion granulation after mixing the modified metal oxide with the first antistatic agent; wherein the modified metal oxide is selected from at least one of modified nano zinc oxide, modified nano tin oxide, modified nano antimony oxide, and modified silicon dioxide;

[0037] Based on the total weight of component B, the content of the polyetheramine is 35-50 wt%, the content of the chain extender is 35-50 wt%, the content of the second antistatic agent is 10-16 wt%, and the content of the auxiliary agent is 1-5 wt%.

[0038] Preferably, in the second antistatic agent, the molar ratio of the modified metal oxide to the first antistatic agent is 1:1-5.

[0039] Preferably, based on the total weight of component A, the isocyanate content is 50-60 wt%, the first antistatic agent content is 8-10 wt%, the polyol content is 25-35 wt%, and the diluent content is 5-7 wt%. The inventors have found that, using this preferred embodiment, the prepared polyurea elastomer exhibits superior mechanical and electrostatic properties.

[0040] Preferably, based on the total weight of component B, the content of the polyetheramine is 45-50 wt%, the content of the chain extender is 35-40 wt%, the content of the second antistatic agent is 14-16 wt%, and the content of the additives is 1-3 wt%. The inventors have discovered that, using this preferred embodiment, polyurea elastomers with superior mechanical and electrostatic conductivity can be prepared.

[0041] According to a particularly preferred embodiment of the present invention, the second antistatic agent is prepared by a method comprising the following steps:

[0042] S1. In the presence of a solvent, a metal oxide and a coupling agent are reacted to obtain a modified metal oxide.

[0043] S2. In the presence of phosphoric acid, the modified metal oxide is melt-blended with the first antistatic agent, and the resulting mixture is extruded, granulated, and then crushed.

[0044] Preferably, in step S1, the metal oxide is selected from at least one of nano zinc oxide, nano tin oxide, nano antimony oxide, and silicon dioxide.

[0045] Preferably, in step S1, the coupling agent is selected from at least one of titanate coupling agents, silane coupling agents, and aluminate coupling agents.

[0046] Preferably, in step S1, the solvent is selected from anhydrous ethanol, isopropanol, polyethylene glycol, or ethylene glycol.

[0047] Preferably, in step S1, the conditions for the contact reaction include at least: a temperature of 70-80°C and a time of 3-6 hours.

[0048] The present invention does not have any particular requirements for the specific operation methods of melt blending and extrusion granulation, and can adopt methods known in the art. For example, the present invention performs melt blending in a mixer and extrusion granulation in a twin-screw extruder.

[0049] The present invention does not have any special requirements for the operation method of the pulverization, as long as it can meet the requirements of the present invention. For example, the present invention uses a three-roll mill to grind the particles to obtain the second antistatic agent with an average particle size of ≤50μm.

[0050] Preferably, the first antistatic agent is selected from at least one of polyether ester, polyoxyethylene-epoxychloropropane copolymer, polyether ester amide, methoxy polyethylene glycol-(meth)acrylic acid copolymer, and polyether ester imide.

[0051] More preferably, the first antistatic agent is selected from at least one of Ciba Specialty Chemicals' Iragastat P22, Arkema's Pebax 4011, Arkema's PEBAX MV1041, Arkema's PEBAX MV1074, Arkema's PEBAX MV3000, Arakawa's AE-1000, and Arakawa's AE-5000.

[0052] Preferably, the isocyanate is selected from at least one of diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-2,2′-diisocyanate, polymethylene polyphenyl polyisocyanate, and liquefied diphenylmethane diisocyanate.

[0053] Preferably, the polyol is selected from at least one of polyethylene glycol, polytetrahydrofuran glycol, polyoxypropylene ether polyol, polyadipate diol, polypropylene glycol, polycaprolactone polyol, and polycarbonate diol.

[0054] According to a particularly preferred embodiment of the present invention, the polyol is a combination of polyoxypropylene ether polyol, polycaprolactone diol, and polyadipate diol in a weight ratio of 1:1-2:2-3. The inventors have found that this preferred embodiment perfectly achieves the goal of improving the electrostatic conductivity of polyurea elastomer while ensuring good tensile and tear strength.

[0055] Preferably, the number average molecular weight of the polyethylene glycol is 400-2000, the number average molecular weight of the polytetrahydrofuran glycol is 250-2000, the number average molecular weight of the polyoxypropylene ether polyol is 250-2000, the number average molecular weight of the polyadipate diol is 400-2000, the number average molecular weight of the polypropylene glycol is 400-2000, the number average molecular weight of the polycaprolactone polyol is 400-2000, and the number average molecular weight of the polycarbonate diol is 400-2000.

[0056] Preferably, the diluent is selected from at least one of toluene-diphenyl phosphate, 2-ethylhexyl diphenyl ester, propylene carbonate, ethyl carbonate, dibutyl phthalate, 2-chloroethyl ester, and acetone.

[0057] Preferably, the polyetheramine is selected from at least one of the following: Huntsman's JEFFAMINE D-230, Huntsman's D-400, Huntsman's T430, Huntsman's D-2000, Huntsman's XTJ-510, Huntsman's ED600, Huntsman's ED900, Huntsman's ED2003, Huntsman's T3000, Huntsman's T5000, Huntsman's SD2001, and Huntsman's ST404.

[0058] Preferably, the chain extender is selected from at least one of diethyltoluenediamine, dimethylthiotoluenediamine, N,N-dialkylmethyldiamine, 1,4-cyclohexanediamine, N,N-dialkylphenyldiamine, isophoronediamine, Huntsman's Jefflink 555, Huntsman's Jefflink 754, Dolphtec's Clearlink 1000, and Wanhua Chemical's Unilink 4200.

[0059] Preferably, the additive is selected from at least one of anti-settling agents, wetting and dispersing agents, defoamers, and ultraviolet absorbers.

[0060] Preferably, the anti-settling agent is selected from at least one of organobentonite, fumed silica, polyamide wax, and polyethylene wax.

[0061] Preferably, the wetting and dispersing agent is selected from at least one of BYK P104, BYK 410, and BYK W980 from BYK Corporation.

[0062] Preferably, the defoamer is selected from at least one of BYK A530, BYK A535, and BYK 065 from BYK Inc.

[0063] Preferably, the ultraviolet absorber is selected from at least one of BASF's UV-531, BASF's UV-326, BASF's UV-328, and BASF's UV-329.

[0064] As previously described, a second aspect of the present invention provides a method for preparing a conductive and explosion-proof polyurea elastomer, wherein the method utilizes the components of the composition described in the first aspect, comprising:

[0065] (1) The first antistatic agent is subjected to dehydration treatment I with a polyol to obtain a first mixture, and the first mixture, isocyanate, and diluent are reacted I to obtain a prepolymer; and

[0066] The polyetheramine and chain extender are subjected to dehydration treatment II to obtain a second mixture. The second mixture, the second antistatic agent and the additives are then subjected to first dispersion and ultrasonic dispersion in sequence to obtain a third mixture.

[0067] (2) Mix the prepolymer and the third mixture.

[0068] Preferably, in step (1), the conditions of the dehydration treatment I and the dehydration treatment II are the same or different, and the conditions of the dehydration treatment I and the dehydration treatment II each independently include: a stirring speed of 100-600 rpm, a temperature of 100-130°C, a vacuum degree of negative pressure of 0.01 MPa to negative pressure of 0.2 MPa, and a time of 2-3 hours.

[0069] Preferably, in step (1), the conditions for reaction I include at least: a temperature of 80-90°C and a time of 2-4 hours.

[0070] Preferably, in step (1), the conditions for the first dispersion include at least: a stirring speed of 400-1400 rpm and a time of 1-3 h.

[0071] Preferably, in step (1), the conditions for ultrasonic dispersion include at least: an ultrasonic frequency of 20-80 kHz, a stirring speed of 100-600 rpm, and a time of 20-30 h.

[0072] Preferably, in step (2), the volume ratio of the prepolymer to the third mixture is 1:1.

[0073] The present invention does not have any special requirements for the specific operation method of the mixture I, as long as it meets the requirements of the present invention. For example, the prepolymer and the third mixture in the present invention can be directly mixed in the spraying equipment and then sprayed for use. The temperature of the spraying equipment is ≥65℃ and the dynamic pressure is ≥13.8MPa.

[0074] As previously described, a third aspect of the present invention provides a conductive and explosion-proof polyurea elastomer prepared by the method described in the second aspect.

[0075] As previously described, the fourth aspect of the present invention provides the application of the electrostatically conductive and explosion-proof polyurea elastomer described in the third aspect in petrochemical equipment and buildings.

[0076] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used are commercially available products.

[0077] Metal oxide: Nano antimony dioxide, purity 99.8%, purchased from Hunan Loudi Huaxing Antimony Industry;

[0078] Metal oxide: Nano tin oxide, HN-Sn20, purchased from Hangzhou Hengna New Materials Co., Ltd.;

[0079] Metal oxide: nano zinc oxide, purchased from Luthai Nanotechnology Co., Ltd.

[0080] Silane coupling agent: brand name A-187, purchased from Momentive Corporation;

[0081] Titanate coupling agent: brand name NDZ-311W, purchased from Hangzhou Jessica Chemical Co., Ltd.;

[0082] First antistatic agent 1: PEBAX MV1074, purchased from Arkema, France;

[0083] First antistatic agent 2: AE-1000, purchased from Arakawa Co., Ltd., Japan;

[0084] Polyol: Polyoxypropylene ether polyol, number average molecular weight 1000, purchased from Dow Chemical Company;

[0085] Polyol: Polyoxypropylene ether polyol, number average molecular weight 2000, purchased from Dow Chemical Company;

[0086] Polyol: Polycaprolactone diol, number average molecular weight 1000, brand name PCL1000, purchased from Daicel.

[0087] Polyol: Poly(adipate diol), molecular weight 1000, purchased from Wuhan Huaxiang Kejie Co., Ltd.

[0088] Polyol: Polytetrahydrofuran ether diol, number average molecular weight 2000, purchased from Mitsubishi Chemical Corporation;

[0089] Isocyanate: diphenylmethane-2,4′-diisocyanate, purchased from Wanhua Chemical Company;

[0090] Isocyanate: Diphenylmethane-4,4′-diisocyanate, purchased from Wanhua Chemical Company;

[0091] Isocyanate: Polymethylene polyphenyl polyisocyanate, brand name PM200, purchased from Wanhua Chemical Company;

[0092] Diluent: Propylene carbonate, purchased from Shida Shenghua Company;

[0093] Polyetheramine: T403, purchased from Huntsman Corporation;

[0094] Polyetheramine: T5000, purchased from Huntsman Corporation;

[0095] Polyetheramine: D2000, purchased from Huntsman Corporation;

[0096] Polyetheramine: D230, purchased from Huntsman Corporation;

[0097] Chain extender: dimethyltoluene diamine, purchased from Yari Chemical Co., Ltd.;

[0098] Chain extender: Jefflink 754, purchased from Huntsman Corporation;

[0099] Chain extender: dimethylthiotoluene diamine, purchased from Yari Chemical Co., Ltd.;

[0100] Anti-settling agent: bentonite, purchased from Guangzhou Hongyi Company;

[0101] Wetting and dispersing agent: BYK P104, purchased from BYK Company;

[0102] Defoamer: BYK A530, purchased from BYK Company;

[0103] UV absorber: UV-328, purchased from BASF;

[0104] In the following example, the spray painting machine is model H-XP3, purchased from Graco.

[0105] Substrate: Polyoxyethylene board, purchased from Dezhou Ruihuan Company;

[0106] In the following examples, ethylene glycol is an analytical chemical reagent;

[0107] In the following examples, each part by weight represents 10g.

[0108] Preparation Example 1

[0109] This preparation example illustrates the preparation method of the second antistatic agent (modified nano-antimony dioxide composite polyether antistatic agent).

[0110] 2 kg of nano-antimony dioxide, 80 g of silane coupling agent and 6 L of ethylene glycol were added to a reaction vessel and stirred at 200 rpm for 30 min at 70 °C. After cooling to room temperature, the mixture was filtered, and the filtered solid material was added to 4 L of water and stirred at 600 rpm. After dispersion at an ultrasonic frequency of 30 kHz for 4 h, the mixture was centrifuged at 30,000 rpm for 10 min. The solid obtained by centrifugation was dried at 80 °C for 60 min to obtain modified nano-antimony dioxide.

[0111] At room temperature, the modified nano-antimony dioxide obtained above was mixed with the first antistatic agent 1 at a molar ratio of 1:2 and then melt-blended in a mixer at a melt-blending temperature of 160°C. The resulting mixture was then extruded and granulated in a twin-screw extruder at a screw temperature of 180°C, a screw speed of 40 rpm, a mixing time of 5 min, a die temperature of 200°C, air cooling, and a granulation turntable speed of 20 rpm. Finally, the mixture was ground in a three-roll mill to a second antistatic agent A1 with an average particle size of 50 μm.

[0112] Preparation Example 2

[0113] This preparation example illustrates the preparation method of the second antistatic agent (modified nano-tin oxide composite polyether antistatic agent).

[0114] 2 kg of nano-tin oxide, 80 g of titanate coupling agent and 6 L of ethylene glycol were added to a reaction vessel and stirred at 200 rpm for 20 min at 75 °C. After cooling to room temperature, the mixture was filtered, and the filtered solid was added to 4 L of water and stirred at 600 rpm. After dispersion at an ultrasonic frequency of 30 kHz for 4 h, the mixture was centrifuged at 30,000 rpm for 10 min. The solid obtained by centrifugation was dried at 85 °C for 55 min to obtain modified nano-tin oxide.

[0115] At room temperature, the modified nano-tin oxide obtained above was mixed with the first antistatic agent 2 at a molar ratio of 1:2 and then melt-blended in a mixer at a melt-blending temperature of 160°C. The resulting mixture was then poured into a twin-screw extruder for extrusion granulation. The extruder screw temperature was 180°C, the screw speed was 40 rpm, the mixing time was 5 min, the die temperature was 200°C, air cooling was used, the granulation turntable speed was 20 rpm, and the mixture was then ground in a three-roll mill to a second antistatic agent A2 with an average particle size of 50 μm.

[0116] Preparation Example 3

[0117] This preparation example illustrates the preparation method of the second antistatic agent (modified nano zinc oxide composite polyether antistatic agent).

[0118] 2 kg of nano zinc oxide, 80 g of titanate coupling agent and 6 L of ethylene glycol were added to a reaction vessel and stirred at 200 rpm for 40 min at 80 °C. After cooling to room temperature, the mixture was filtered, and the filtered solid material was added to 4 L of water and stirred at 600 rpm. After dispersion at an ultrasonic frequency of 30 kHz for 4 h, the mixture was centrifuged at 20,000 rpm for 20 min. The solid obtained by centrifugation was dried at 90 °C for 50 min to obtain modified nano zinc oxide.

[0119] At room temperature, the modified nano zinc oxide obtained above was mixed with the first antistatic agent 1 at a molar ratio of 1:2 and then melt-blended in a mixer at a melt-blending temperature of 160°C. The resulting mixture was then poured into a twin-screw extruder for extrusion granulation. The extruder screw temperature was 180°C, the screw speed was 40 rpm, the mixing time was 5 min, the die temperature was 200°C, air cooling was used, the granulation turntable speed was 20 rpm, and the mixture was then ground in a three-roll mill to produce the second antistatic agent A3 with an average particle size of 50 μm.

[0120] Example 1

[0121] This embodiment provides a method for preparing a conductive and explosion-proof polyurea elastomer, including the following steps:

[0122] (1) Add polyol to the first antistatic agent 1, stir and heat to 120°C at 200 rpm, dehydrate for 2 hours under vacuum of -0.1 MPa to obtain the first mixture, then release the vacuum, cool to 60°C, add isocyanate and diluent under nitrogen protection, react at 80°C for 3 hours, after the reaction is completed, cool to below 40°C and filter to obtain the prepolymer;

[0123] Under conditions of 100℃ and -0.1MPa vacuum, polyetheramine and chain extender were stirred and dehydrated at 200rpm for 2 hours to obtain a second mixture. After the vacuum was released and the temperature was lowered to 60℃, 150g of the second antistatic agent A1 and the additives were added. The mixture was stirred and dispersed at 1400rpm for 2 hours, and then stirred and dispersed at 200rpm for 24 hours under ultrasonic frequency of 30KHz. The mixture was then filtered to obtain a third mixture.

[0124] (2) The prepolymer and the third mixture obtained above are sprayed onto the substrate at a volume ratio of 1:1 using a spraying equipment (Graco H-XP3, temperature 70℃, dynamic pressure 13.8MPa) to obtain a substrate containing conductive and explosion-proof polyurea elastomer S1.

[0125] Unless otherwise specified, Examples 2-6 were carried out using the same process as Example 1, except that the conductive and explosion-proof polyurea elastomer formulations used were different, as detailed in Table 1.

[0126] Comparative Example 1

[0127] The conductive and explosion-proof polyurea elastomer was prepared according to the method of Example 1, except that the first antistatic agent was not added in step (1).

[0128] Comparative Example 2

[0129] The conductive and explosion-proof polyurea elastomer was prepared according to the method of Example 1, except that no second antistatic agent was added in step (1).

[0130] Comparative Example 3

[0131] The conductive and explosion-proof polyurea elastomer was prepared according to the method of Example 1, except that in step (1), an equal mass of PEBAX MV1074 was used to replace the second antistatic agent A1.

[0132] Comparative Example 4

[0133] The conductive and explosion-proof polyurea elastomer was prepared according to the method of Example 1, except that in step (1), an equal mass of AE-1000 was used to replace the second antistatic agent A1.

[0134] Table 1

[0135]

[0136]

[0137] Table 1 (continued)

[0138]

[0139]

[0140] Test case

[0141] Under the conditions of room temperature and relative humidity of 60±10%, the matrix containing conductive and explosion-proof polyurea elastomer obtained in the examples and comparative examples was placed for 7 days and then the performance was tested, including tensile properties, elongation at break, tear strength, resistance to gas explosion and surface resistivity. The specific test results are shown in Table 2.

[0142] Among them, tensile strength and elongation at break were tested according to the test procedures specified in GB / T528-2009;

[0143] Tear strength was tested according to the test procedure specified in GB / T529;

[0144] The gas explosion resistance performance was tested according to the test procedures specified in T / CIESC 0019-2021;

[0145] Surface resistivity was tested according to the test procedure specified in GB / T16906.

[0146] Table 2

[0147]

[0148] As can be seen from the results in Table 2, the polyurea elastomer prepared by the method provided in this invention can improve mechanical properties while ensuring electrostatic conductivity.

[0149] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An electrostatically conductive blast resistant polyurea elastomer composition characterized in that, The composition comprises component A and component B in a weight ratio of 1:0.9-1; Component A contains the following components, which may be stored independently or in combination: isocyanate, polyol, first antistatic agent, and diluent; The isocyanate contains at least two isocyanate groups; The first antistatic agent is a polyether antistatic agent; The polyol is a polyether polyol and / or a polyester polyol, and the number average molecular weight of the polyol is 200-2000. Based on the total weight of component A, the content of isocyanate is 50-65 wt%, the content of the first antistatic agent is 8-10 wt%, the content of polyol is 25-40 wt%, and the content of diluent is 0-10 wt%. Component B contains the following components, which may be stored independently or in combination: polyetheramine, chain extender, second antistatic agent, and additives; The second antistatic agent is obtained by extruding and granulating a mixture of a modified metal oxide and the first antistatic agent; wherein the modified metal oxide is selected from at least one of modified nano zinc oxide, modified nano tin oxide, and modified nano antimony oxide; Based on the total weight of component B, the content of the polyetheramine is 35-50 wt%, the content of the chain extender is 35-50 wt%, the content of the second antistatic agent is 10-16 wt%, and the content of the auxiliary agent is 1-5 wt%.

2. The composition of claim 1, wherein, In the second antistatic agent, the molar ratio of the modified metal oxide to the first antistatic agent is 1:1-5.

3. The composition according to claim 1 or 2, wherein, The first antistatic agent is selected from at least one of polyether ester, polyoxyethylene-epoxychloropropane copolymer, polyether ester amide, and methoxy polyethylene glycol-(meth)acrylic acid copolymer.

4. The composition according to claim 1 or 2, wherein, The first antistatic agent is selected from at least one of Ciba Specialty Chemicals' Iragastat P22, Arkema's Pebax 4011, Arkema's PEBAX MV1041, Arkema's PEBAX MV1074, Arkema's PEBAX MV3000, Arakawa's AE-1000, and Arakawa's AE-5000.

5. The composition of claim 1 or 2, wherein, The isocyanate is selected from at least one of diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-2,2′-diisocyanate, polymethylene polyphenyl polyisocyanate, and liquefied diphenylmethane diisocyanate.

6. The composition of claim 1 or 2, wherein, The polyol is selected from at least one of polyethylene glycol, polytetrahydrofuran glycol, polyoxypropylene ether polyol, polyadipate diol, polypropylene glycol, polycaprolactone polyol, and polycarbonate diol.

7. The composition of claim 1 or 2, wherein, The diluent is selected from at least one of toluene-diphenyl phosphate, propylene carbonate, ethyl carbonate, dibutyl phthalate, and acetone; and / or The polyetheramine is selected from at least one of Huntsman's JEFFAMINE D-230, Huntsman's D-400, Huntsman's T430, Huntsman's D-2000, Huntsman's XTJ-510, Huntsman's ED600, Huntsman's ED900, Huntsman's ED2003, Huntsman's T3000, Huntsman's T5000, Huntsman's SD2001, and Huntsman's ST404; and / or The chain extender is selected from at least one of diethyltoluenediamine, dimethylthiotoluenediamine, N,N-dialkylmethyldiamine, 1,4-cyclohexanediamine, N,N-dialkylphenyldiamine, isophoronediamine, Huntsman's Jefflink 555, Huntsman's Jefflink 754, Dolphtec's Clearlink 1000, and Wanhua Chemical's Unilink 4200.

8. The composition of claim 1 or 2, wherein, The additive is selected from at least one of anti-settling agents, wetting and dispersing agents, defoamers, and ultraviolet absorbers.

9. The composition of claim 8, wherein, The anti-settling agent is selected from at least one of organic bentonite, fumed silica, polyamide wax, and polyethylene wax.

10. A method of making an electrostatically conductive blast resistant polyurea elastomer, characterized by, This method involves mixing the components of the composition according to any one of claims 1-9, including: (1) The first antistatic agent and the polyol are subjected to dehydration treatment I to obtain a first mixture, and the first mixture, isocyanate and diluent are reacted I to obtain a prepolymer; and The polyetheramine and chain extender are subjected to dehydration treatment II to obtain a second mixture. The second mixture, the second antistatic agent and the additives are then subjected to first dispersion and ultrasonic dispersion in sequence to obtain a third mixture. (2) Mix the prepolymer and the third mixture.

11. The method of claim 10, wherein, In step (1), the conditions of the dehydration treatment I and the dehydration treatment II are the same or different, and the conditions of the dehydration treatment I and the dehydration treatment II each independently include: a stirring speed of 100-600 rpm, a temperature of 100-130℃, a vacuum degree of negative pressure of 0.01MPa to negative pressure of 0.2MPa, and a time of 2-3 hours.

12. The method of claim 10 or 11, wherein, In step (1), the conditions for reaction I include at least the following: temperature of 80-90°C and time of 2-4 hours.

13. The method of claim 10 or 11, wherein, In step (1), the conditions for the first dispersion include at least: a stirring speed of 400-1400 rpm and a time of 1-3 h; and / or In step (1), the conditions for ultrasonic dispersion include at least the following: ultrasonic frequency of 20-80kHz, stirring speed of 100-600rpm, and time of 20-30h.

14. The conductive and explosion-proof polyurea elastomer prepared by the method according to any one of claims 10-13.

15. The application of the electrostatically conductive and explosion-proof polyurea elastomer of claim 14 in petrochemical equipment and buildings.

Images