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CN-118359986-B - Halogen-free flame-retardant polyurea protective coating and application thereof

CN118359986BCN 118359986 BCN118359986 BCN 118359986BCN-118359986-B

Abstract

The invention provides a halogen-free flame-retardant polyurea protective coating which comprises a component A and a component B, wherein the component A is a semi-prepolymer prepared by reacting first polyether polyol with aromatic isocyanate, and the component B comprises, by weight, 30-50 parts of second polyether polyol, 20-30 parts of amine chain extender, 15-20 parts of halogen-free flame retardant, 0.2-0.5 part of coupling agent and 0.2-0.5 part of catalyst. The invention provides a flame-retardant polyurea protective material which can be used in petrochemical industry, and has excellent mechanical properties and high-efficiency and environment-friendly flame-retardant properties.

Inventors

  • ZHANG SHENG
  • LIU QINYONG
  • GU XIAOYU
  • SUN JUN

Assignees

  • 北京化工大学

Dates

Publication Date
20260505
Application Date
20240506

Claims (10)

  1. 1. The halogen-free flame-retardant polyurea protective coating comprises a component A and a component B, and is characterized in that the component A is a semi-prepolymer prepared by reacting first polyether polyol with aromatic isocyanate, and the component B comprises, by weight, 30-50 parts of second polyether polyol, 20-30 parts of amine chain extender, 31-35 parts of halogen-free flame retardant, 0.2-0.5 part of coupling agent and 0.2-0.5 part of catalyst; the molecular formula of the halogen-free flame retardant is as follows: 。
  2. 2. the halogen-free flame retardant polyurea protective coating of claim 1, wherein the first polyether polyol is at least one of polytetrahydrofuran ether polyol and polyoxypropylene ether polyol, and the second polyether polyol is at least one of difunctional polyether polyol and trifunctional polyether polyol.
  3. 3. The halogen-free flame retardant polyurea protective coating of claim 2, wherein the first polyether polyol has a molecular weight of 1000-2000 and the second polyether polyol has a molecular weight of 1000-4000.
  4. 4. The halogen-free flame retardant polyurea protective coating according to any one of claims 1-3, wherein the component a and the component B are both liquid phase components, and the volume ratio of the component a to the component B is a=1:1.
  5. 5. The halogen-free flame retardant polyurea protective coating of claim 2, wherein the semi-prepolymer is prepared by the following method: s101, heating the first polyether polyol to 100-120 ℃ in an inert environment in a reaction vessel and maintaining stirring; S102, enabling the reaction container to be in a negative pressure environment, and maintaining the negative pressure environment for a preset time; S103, maintaining a negative pressure environment, and reducing the temperature of the first polyether polyol in the reaction container to 50-60 ℃; S104, adding a proportioning amount of isocyanate into a reaction container, and heating a reaction system of the first polyether polyol and the isocyanate to 80-90 ℃; S105 is reacted for 2-3 hours to obtain the semi-prepolymer.
  6. 6. The halogen-free flame retardant polyurea protective coating of any one of claims 1 or 5, wherein NCO% = 15-20% in the semi-prepolymer.
  7. 7. The halogen-free flame retardant polyurea protective coating of claim 1, wherein the halogen-free flame retardant is prepared by the following method: S201, according to parts by weight, dissolving 10-20 parts of p-formylphenylboric acid and 10-15 parts of tris (hydroxymethyl) aminomethane in a solvent to obtain a first reaction system; s202, heating the first reaction system to 65-75 ℃, and stirring and reacting for 40-120min to obtain a second reaction system; S203, dissolving 20-40 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a solvent, dripping the solution into a second reaction system, maintaining the reaction temperature at 65-75 ℃, and continuously stirring the solution for reaction for 4-8 hours to obtain a third reaction system; And S204, carrying out suction filtration on the third reaction system, washing by adopting the solvent in S201, and drying to obtain the halogen-free flame retardant.
  8. 8. The halogen-free, flame retardant polyurea protective coating of claim 7, wherein the solvent is absolute ethanol.
  9. 9. The halogen-free flame retardant polyurea protective coating according to any one of claims 1 or 7, wherein the halogen-free flame retardant comprises 20-30% by mass of the B component.
  10. 10. Use of a halogen-free flame retardant polyurea protective coating according to any one of claims 1 to 9 in the fields of tank protection, ballistic coating, car body protection, building waterproofing, pipe corrosion protection and hull protection.

Description

Halogen-free flame-retardant polyurea protective coating and application thereof Technical Field The invention relates to the technical field of polymer flame-retardant modification, in particular to a halogen-free flame-retardant polyurea protective coating and application thereof. Background Polyurea (PUA) is widely used as a coating excellent in properties in the fields of protection of vehicles and airplanes, corrosion protection of storage tanks, waterproofing of buildings, and the like, due to its excellent mechanical properties, corrosion resistance, wear resistance, water resistance, and the like. The spray-type polyurea is a coating formed by reacting an isocyanate component (A component) and an amino compound component (B component), and the spray-type polyurea integrates the advantages of the coating, the rubber, the plastic and other anti-corrosion materials, and is one of the most advanced anti-corrosion technologies internationally at present. The spray polyurea technology adopts amine terminated polyether and amine chain extender as active hydrogen components, reacts with isocyanate, can be rapidly cured at room temperature, and has the advantages of no solvent, high mechanical strength, high construction speed, aging resistance and the like. However, polyurea itself is extremely flammable, limiting Oxygen Index (LOI) is only about 21%, and a large amount of molten drops and toxic smoke are generated during combustion, and a large amount of molten drops with fire cause scalding of personnel and rapid diffusion of fire, and toxic smoke can cause suffocation of personnel, so that improvement of flame retardant property of polyurea itself while maintaining excellent mechanical properties is of great significance. In the prior art, two main approaches are provided for improving the flame retardance of the spray polyurea material: Firstly, the chemical structure of the polyurea is changed, and flame retardant elements such as phosphorus, nitrogen, silicon and the like are generally introduced into the molecular chain of the polyurea. And secondly, adding a flame retardant containing a flame retardant element into the polyurea material. The latter has better practicability and economy, and is a common method for flame-retardant modification of spray polyurea. However, the existing polyurea materials obtained by flame retardant modification, especially polyurea coatings, still have unsatisfactory flame retardant effect, and the addition of the flame retardant always causes the problem of remarkable reduction of mechanical properties, which affects the application of the flame retardant polyurea coatings. Disclosure of Invention In order to solve the defects in the prior art, the invention provides a halogen-free flame-retardant polyurea protective coating, which comprises a component A and a component B, wherein the component A is a semi-prepolymer prepared by reacting first polyether polyol with aromatic isocyanate. The component B comprises, by weight, 30-50 parts of a second polyether polyol, 20-30 parts of an amine chain extender, 31-35 parts of a halogen-free flame retardant, 0.2-0.5 part of a coupling agent and 0.2-0.5 part of a catalyst. The molecular formula of the halogen-free flame retardant is as follows: further, the first polyether polyol is at least one of polytetrahydrofuran ether polyol and polyoxypropylene ether polyol. The second polyether polyol is at least one of difunctional polyether polyol and trifunctional polyether polyol. Further, the first polyether polyol has a molecular weight of 1000 to 2000. The molecular weight of the second polyether polyol is 1000-4000. Further, the A component and the B component are both liquid phase components. The volume ratio of the component A to the component B is that the component A is that the component B is=1:1. Further, the semi-prepolymer is prepared by the following method: s101, heating the first polyether polyol to 100-120 ℃ in an inert environment in a reaction vessel and maintaining stirring. S102, making the reaction container become a negative pressure environment, and maintaining the negative pressure environment for a preset time. S103, maintaining a negative pressure environment, and reducing the temperature of the first polyether polyol in the reaction vessel to 50-60 ℃. S104, adding a proportioning amount of isocyanate into a reaction vessel, and heating a reaction system of the first polyether polyol and the isocyanate to 80-90 ℃. S105 is reacted for 2-3 hours to obtain the semi-prepolymer. Further, the semi-prepolymer has an NCO% content of 15 to 20%. Further, the halogen-free flame retardant is prepared by the following method: S201, according to parts by weight, dissolving 10-20 parts of p-formylphenylboric acid and 10-15 parts of tris (hydroxymethyl) aminomethane in a solvent to obtain a first reaction system. S202, heating the first reaction system to 65-75 ℃, and stirring and reacting for 40-120min to obtain a second