阅读说明：本技术 一种抗静电防爆聚脲材料及其制备方法和应用 (Antistatic and explosion-proof polyurea material and preparation method and application thereof ) 是由 王宝柱 李灿刚 王伟 邵春妍 温喜梅 于 2020-06-29 设计创作，主要内容包括：本发明提出了一种抗静电防爆聚脲材料及其制备方法和应用,包括A组分和B组分,A组分包括以下原料：二异氰酸酯、聚酯多元醇和碳纳米管；B组分包括以下原料：聚酯多元醇、端氨基扩链剂以及助剂；本发明的抗静电防爆聚脲材料,包括碳纳米管,碳纳米管具有优异的力学性能、电学性能、光学性能、吸附性能等,在聚脲材料中添加少量的碳纳米管,可以提高聚脲材料的拉伸强度和撕裂强度进而提高材料力学性能以达到防爆抗冲击的作用,还可以明显降低聚脲材料的表面电阻率以达到抗静电的效果。(The invention provides an antistatic explosion-proof polyurea material and a preparation method and application thereof, wherein the antistatic explosion-proof polyurea material comprises a component A and a component B, wherein the component A comprises the following raw materials: diisocyanate, polyester polyol and carbon nanotubes; the component B comprises the following raw materials: polyester polyol, an amino-terminated chain extender and an auxiliary agent; the anti-static and anti-explosion polyurea material comprises the carbon nano tubes, the carbon nano tubes have excellent mechanical property, electrical property, optical property, adsorption property and the like, a small amount of carbon nano tubes are added into the polyurea material, the tensile strength and the tearing strength of the polyurea material can be improved, the mechanical property of the material is further improved, the anti-explosion and anti-impact effects are achieved, and the surface resistivity of the polyurea material can be obviously reduced, so that the anti-static effect is achieved.)

1. An antistatic explosion-proof polyurea material is characterized in that: the paint comprises a component A and a component B, wherein the component A comprises the following raw materials: diisocyanate, polyester polyol and carbon nanotubes; the component B comprises the following raw materials: polyester polyol, an amino-terminated chain extender and an auxiliary agent.

2. The antistatic explosion-proof polyurea material according to claim 1, wherein: the carbon nano-tube comprises a single-wall terminal amino carbon nano-tube or a multi-wall terminal amino carbon nano-tube.

3. The antistatic explosion-proof polyurea material according to claim 1, wherein: the carbon nanotube has a diameter of 6 to 12nm and a length of 20 to 50 μm.

4. The antistatic explosion-proof polyurea material according to claim 1, wherein: the diisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, trimethyl hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and tetramethylxylylene diisocyanate; the polyester polyol comprises one or more of polycaprolactone diol, polyethylene glycol adipate diol, polyhexamethylene glycol adipate diol and polycarbonate diol; the relative molecular weight of the polyester polyol is 500-4000, and the average functionality is 2.0-2.8; the amino-terminated chain extender comprises one or more of 3, 5-diethyltoluenediamine, 3, 5-dimethylthiotoluenediamine, 2, 4-diamino-3, 5-dimethylthiochlorobenzene, 4 '-bis-sec-butylaminodiphenylmethane, N, -dialkylphenylenediamine, 2, 4-diamino-3-methylthio-5-propyltoluene, 3' -dimethyl-4, 4 '-diaminodicyclohexylmethane, 4' -bis-sec-butylaminodicyclohexylmethane and 3,3 '-dimethyl-4, 4' -bis-sec-butylaminodicyclohexylmethane.

5. The antistatic explosion-proof polyurea material according to claim 1, wherein: the auxiliary agent comprises at least one of a catalyst, an ultraviolet absorbent, a light stabilizer, an adhesion promoter and a water removal agent.

6. The antistatic explosion-proof polyurea material according to claim 5, wherein: the catalyst comprises at least one of tertiary amine catalyst and organic metal compound catalyst;

the tertiary amine catalyst comprises one of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N ' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N, N ' -diethylpiperazine, triethanolamine, N, N ' -dimethylethanolamine and N, N ' -dimethylpyridine;

the organic metal compound catalyst comprises one of dibutyltin dilaurate, stannous octoate, lead isooctanoate, zinc isooctanoate, bismuth isooctanoate, tetrabutyl titanate and tetraisopropyl titanate;

the ultraviolet absorbent comprises one or more of 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3, 5 bis (a, a-dimethylbenzyl) phenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-phenyl) -5-chlorobenzotriazole and 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole;

the light stabilizer comprises one or more of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, poly (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidyl ethanol) succinate and bis (2,2,6, 6-tetramethyl-piperidyl) sebacate;

the adhesion promoter comprises a silane coupling agent, and the silane coupling agent comprises one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, aniline triethoxysilane, aniline propyltriethoxysilane, gamma-glycidyl ether oxypropyltrimethoxysilane, beta- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-isocyanate propyltriethoxysilane;

the water removing agent is a molecular sieve.

7. The antistatic explosion-proof polyurea material according to claim 1, wherein: the volume ratio of the component A to the component B is 1: 1; the mass ratio of diisocyanate, polyester polyol and carbon nano tubes in the component A is 40-60: 38-55: 0.5-2; the mass ratio of the polyester polyol, the amino-terminated chain extender and the auxiliary agent in the component B is 50-60: 30-45: 6-10.

8. A method for preparing the antistatic explosion-proof polyurea material as claimed in any one of claims 1 to 7, characterized in that: the preparation method comprises the steps of preparing a component A and preparing a component B;

wherein, the preparation of the component A comprises the following steps:

s1, adding the carbon nano tube and the polyester polyol after stirring the diisocyanate, heating, and reacting until the NCO content is 16-22% to obtain a component A;

the preparation of the component B comprises the following steps:

and S2, heating and melting the polyester polyol, sequentially adding the amino-terminated chain extender and the auxiliary agent, and uniformly stirring to obtain the component B.

9. The method for preparing an antistatic explosion-proof polyurea material according to claim 8, wherein:

and (3) stirring diisocyanate in the S1, heating to 50-60 ℃, adding the carbon nano tube and the polyester polyol, heating to 85-95 ℃, and reacting until the NCO content is 16-22% to obtain the component A.

10. The application of the antistatic explosion-proof polyurea material as claimed in any one of claims 1 to 7 on the surfaces of petrochemical storage and transportation equipment and radomes.

Technical Field

The invention relates to the technical field of spray polyurea materials, in particular to an antistatic and explosion-proof polyurea material and a preparation method and application thereof.

Background

With the advance of the strategy of petroleum storage in China, China has entered the high-speed growth period of large petrochemical equipment construction. The crude oil, especially the light oil, generates electric charge due to friction in the processes of transportation, mixing, filtering, filling and extraction. When the rate of charge extraction is less than the rate of charge generation, charge accumulation occurs. When the concentration of the volatile oil reaches the explosion limit, the accumulated charges are easy to generate electrostatic sparks to cause explosion, thereby causing huge economic property loss. The accumulation of electric charge can be effectively eliminated by coating the antistatic material on the surface of the equipment, so that accidents are avoided.

The polyurea material has the characteristics of quick curing, high construction efficiency, corrosion resistance, wear resistance, corrosion resistance, impact resistance and the like, and has wide application in the fields of water resistance, corrosion resistance, wear resistance of mines, military protection and the like. In order to make the polyurea material have excellent insulating performance, a large amount of liquid antistatic agent or powder antistatic agent needs to be added into the polyurea material to achieve the antistatic effect. The prior art reports a method for preparing a flexible antistatic material by adding a liquid antistatic agent and a powder antistatic agent into a polyurea material. However, in the polyurea material, the addition of the antistatic material in a large amount causes a decrease in the strength of the polyurea material.

Based on the above defects, there is a need for improvement of the existing antistatic polyurea material to meet the requirements of antistatic and explosion-proof.

Disclosure of Invention

In view of the above, the invention provides an antistatic explosion-proof polyurea material with high tensile strength, high tear strength and low surface resistivity.

The technical scheme of the invention is realized as follows: the invention provides an antistatic and explosion-proof polyurea material: the paint comprises a component A and a component B, wherein the component A comprises the following raw materials: diisocyanate, polyester polyol and carbon nanotubes; the component B comprises the following raw materials: polyester polyol, an amino-terminated chain extender and an auxiliary agent.

On the basis of the above technical solution, preferably, the carbon nanotube includes a single-walled terminal amino carbon nanotube or a multi-walled terminal amino carbon nanotube.

On the basis of the technical scheme, the diameter of the carbon nano tube is 6-12 nm, and the length of the carbon nano tube is 20-50 mu m.

On the basis of the above technical solution, preferably, the diisocyanate includes one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, trimethylhexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate; the polyester polyol comprises one or more of polycaprolactone diol, polyethylene glycol adipate diol, polyhexamethylene glycol adipate diol and polycarbonate diol; the amino-terminated chain extender comprises one or more of 3, 5-diethyltoluenediamine, 3, 5-dimethylthiotoluenediamine, 2, 4-diamino-3, 5-dimethylthiochlorobenzene, 4 '-bis-sec-butylaminodiphenylmethane, N, -dialkylphenylenediamine, 2, 4-diamino-3-methylthio-5-propyltoluene, 3' -dimethyl-4, 4 '-diaminodicyclohexylmethane, 4' -bis-sec-butylaminodicyclohexylmethane and 3,3 '-dimethyl-4, 4' -bis-sec-butylaminodicyclohexylmethane.

On the basis of the above technical scheme, preferably, the auxiliary agent includes at least one of a catalyst, an ultraviolet absorber, a light stabilizer, an adhesion promoter, and a water scavenger.

Further preferably, the catalyst includes at least one of a tertiary amine-based catalyst and an organometallic compound-based catalyst;

the tertiary amine catalyst comprises one of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N ' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N, N ' -diethylpiperazine, triethanolamine, N, N ' -dimethylethanolamine and N, N ' -dimethylpyridine;

the organic metal compound catalyst comprises one of dibutyltin dilaurate, stannous octoate, lead isooctanoate, zinc isooctanoate, bismuth isooctanoate, tetrabutyl titanate and tetraisopropyl titanate;

the ultraviolet absorbent comprises one or more of 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3, 5 bis (a, a-dimethylbenzyl) phenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-phenyl) -5-chlorobenzotriazole and 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole;

the light stabilizer comprises one or more of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, poly (4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidyl ethanol) succinate and bis (2,2,6, 6-tetramethyl-piperidyl) sebacate;

the adhesion promoter comprises a silane coupling agent, and the silane coupling agent comprises one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, aniline triethoxysilane, aniline propyltriethoxysilane, gamma-glycidyl ether oxypropyltrimethoxysilane, beta- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-isocyanate propyltriethoxysilane;

the water removing agent is a molecular sieve.

On the basis of the technical scheme, preferably, the volume ratio of the component A to the component B is 1: 1; the mass ratio of diisocyanate, polyester polyol and carbon nano tubes in the component A is 40-60: 38-55: 0.5-2; the mass ratio of the polyester polyol, the amino-terminated chain extender and the auxiliary agent in the component B is 50-60: 30-45: 6-10.

The invention also provides a preparation method of the antistatic explosion-proof polyurea material, which comprises the preparation of the component A and the preparation of the component B;

wherein, the preparation of the component A comprises the following steps:

s1, adding the carbon nano tube and the polyester polyol after stirring the diisocyanate, heating, and reacting until the NCO content is 16-22% to obtain a component A;

the preparation of the component B comprises the following steps:

and S2, heating and melting the polyester polyol, sequentially adding the amino-terminated chain extender and the auxiliary agent, and uniformly stirring to obtain the component B.

On the basis of the technical scheme, preferably, the diisocyanate in the S1 is stirred and heated to 50-60 ℃, then the carbon nano tube and the polyester polyol are added, the temperature is raised to 85-95 ℃, and the reaction is carried out until the NCO content is 16-22%, so that the component A is obtained.

The invention also provides application of the antistatic explosion-proof polyurea material on the surfaces of petrochemical storage and transportation equipment and radomes.

Compared with the prior art, the antistatic explosion-proof polyurea material has the following beneficial effects:

(1) the anti-static and anti-explosion polyurea material comprises the carbon nano tubes, wherein the carbon nano tubes have excellent mechanical property, electrical property, optical property, adsorption property and the like, and a small amount of carbon nano tubes are added into the polyurea material, so that the tensile strength and the tearing strength of the polyurea material can be improved, the mechanical property of the material can be improved, the anti-explosion and anti-impact effects can be achieved, and the surface resistivity of the polyurea material can be obviously reduced, so that the anti-static effect can be achieved;

(2) the antistatic explosion-proof polyurea material further adopts the single-wall terminal amino carbon nano tube or the multi-wall terminal amino carbon nano tube, and the aminated carbon nano tube can improve the dispersibility and the storage stability of the aminated carbon nano tube in the polyurea material, thereby being beneficial to preparing the polyurea material with high mechanical property and excellent low electrical impedance electrostatic property; meanwhile, amino groups on the surface of the aminated carbon nanotube react with isocyanate to form urea groups with stable structures, so that the urea groups can bear the impact of larger load in the stress process, and the mechanical property of the polyurea material is improved; the long-diameter ratio of the carbon nano tube has larger influence on the mechanical property and the antistatic property of the polyurea material, and the high length-diameter ratio (such as the diameter of 6-12 nm and the length of more than 50 mu m) can improve the antistatic property of the polyurea material, but can reduce the mechanical property of the polyurea material and simultaneously improve the viscosity of the prepolymer of the component A, so that the construction process property is reduced; although the mechanical property of the polyurea material can be improved due to the low length-diameter ratio (such as the diameter of 6-12 nm and the length of less than 20 microns), the contact between the carbon nanotubes in the polyurea material can be reduced, so that a conductive network passage is difficult to form, and the polyurea material has high resistance and poor antistatic property, therefore, in order to balance the mechanical property and the antistatic property, the diameter of the selected aminated carbon nanotube is 6-12 nm, and the length of the selected aminated carbon nanotube is 20-50 microns;

(3) the antistatic explosion-proof polyurea material can be widely applied to the fields of petrochemical storage and transportation equipment, radome protection and the like, and has the characteristics of high strength, corrosion resistance, explosion resistance, low resistivity, excellent antistatic performance and the like.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.