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CN-122011735-A - Pre-composite aerogel modified polyurethane foam insulation board and preparation method thereof

CN122011735ACN 122011735 ACN122011735 ACN 122011735ACN-122011735-A

Abstract

The application discloses a pre-composite aerogel modified polyurethane foaming insulation board and a preparation method thereof, and belongs to the technical field of polyurethane insulation materials. The pre-composite aerogel modified polyurethane foaming insulation board is prepared by foaming a component A and a component B under high pressure and curing and forming in a mold, wherein the component A comprises, by weight, 100 parts of polyol, 8-12 parts of modified silica aerogel powder, 10-15 parts of modified glass fiber, 31-37 parts of composite flame retardant, 4-6 parts of environment-friendly foaming agent, 0.8-1.2 parts of deionized water, 1.2-1.8 parts of composite silicone oil stabilizer and 0.48-0.95 part of composite catalyst, and the component B comprises 130-150 parts of polymeric MDI. The three-dimensional interpenetrating inorganic skeleton, the collaborative polyol system and the polymeric MDI are formed by the coordination of the modified silica aerogel powder and the modified glass fiber in a pre-compounding way, and the comprehensive performance of the heat-insulating board is obviously improved by high-pressure foaming and in-mold curing molding, so that the collaborative balance of heat-insulating performance, flame-retardant performance and mechanical performance is realized.

Inventors

  • Pan Shaoxue
  • WANG CHAO
  • XI HONGLIANG
  • ZHANG YIMING
  • CHEN YU
  • ZHAO GUIDONG
  • WANG HAOZHEN
  • WANG JUNYI
  • SUN WENTAO

Assignees

  • 中建八局(山东)新型材料科技有限公司
  • 中国建筑第八工程局有限公司

Dates

Publication Date
20260512
Application Date
20260320

Claims (10)

  1. 1. The pre-composite aerogel modified polyurethane foaming insulation board is characterized by being prepared by foaming a component A and a component B under high pressure and curing and forming in a mold, wherein the component A comprises, by weight, 100 parts of polyol, 8-12 parts of modified silica aerogel powder, 10-15 parts of modified glass fiber, 31-37 parts of composite flame retardant, 4-6 parts of environment-friendly foaming agent, 0.8-1.2 parts of deionized water, 1.2-1.8 parts of composite silicone oil stabilizer and 0.48-0.95 part of composite catalyst, the component B comprises 130-150 parts of polymeric MDI, and in a reaction system formed by mixing the component A and the component B, the isocyanate index is 1.05-1.15, and the polyol comprises 70-80 parts of flame-retardant aromatic polyether polyol and 20-30 parts of phthalic anhydride polyester polyol.
  2. 2. The pre-composite aerogel modified polyurethane foam insulation board of claim 1, wherein the modified hydrophobic silica aerogel powder is phosphazene-hydroxyapatite whisker in-situ grafting modified hydrophobic silica aerogel powder, and the modified glass fiber is polydopamine-phosphazene flame retardant polyol grafting modified alkali-free chopped glass fiber.
  3. 3. The pre-composite aerogel modified polyurethane foam insulation board of claim 1, wherein the composite flame retardant comprises low-melting-point borosilicate glass powder, organic silicon resin coated ammonium polyphosphate, zircon powder and melamine cyanurate, and the mass ratio of the low-melting-point borosilicate glass powder to the organic silicon resin coated ammonium polyphosphate, the zircon powder to the melamine cyanurate is (15-20): 10-12): 3-5): 2-3.
  4. 4. The pre-composite aerogel modified polyurethane foam insulation board of claim 2, wherein the phosphazene fluorosilane-hydroxyapatite whisker in-situ grafting modified hydrophobic silica aerogel powder is prepared by firstly carrying out in-situ hydroxyl grafting on aerogel powder by adopting a fluorosilane coupling agent containing an phosphazene flame retardant group, and then growing hydroxyapatite whiskers on the surface of the aerogel in situ, wherein the length of the hydroxyapatite whiskers is 500-2 mu m, the diameter is 20-50 nm, and the loading amount of the hydroxyapatite whiskers is 3-5% of the mass of the aerogel powder.
  5. 5. The pre-composite aerogel modified polyurethane foam insulation board is characterized in that the polydopamine-phosphazene flame-retardant polyol grafted modified alkali-free chopped glass fiber is prepared by the steps of depositing a dopamine nanometer layer on the surface of the alkali-free chopped glass fiber, bridging the surface of the polydopamine layer through an epoxy silane coupling agent, grafting a phosphorus-nitrogen flame-retardant group-containing polyether polyol on the surface of the polydopamine layer, wherein the hydroxyl value of the phosphorus-nitrogen flame-retardant group-containing polyether polyol is 350-400 mgKOH/g, and the functionality is 3-4.
  6. 6. The pre-composite aerogel modified polyurethane foam insulation board of claim 1, wherein the environment-friendly foaming agent comprises HFO-1234ze, and the composite catalyst comprises 0.4-0.8 part of triethylene diamine and 0.08-0.15 part of delayed organotin in parts by weight.
  7. 7. The pre-composite aerogel modified polyurethane foam insulation board of claim 1, wherein the flame retardant aromatic polyether polyol is phosphorus-containing flame retardant modified polyether polyol, the hydroxyl value of the phosphorus-containing flame retardant modified polyether polyol is 390-450 mgKOH/g, the functionality is 4-5, the hydroxyl value of the phthalic anhydride polyester polyol is 280-320 mgKOH/g, and the functionality is 2-3.
  8. 8. The preparation method of the pre-composite aerogel modified polyurethane foam insulation board as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps: (1) Adding modified aerogel powder and modified glass fiber into absolute ethyl alcohol according to a proportion, performing ultrasonic dispersion for 20-30 min under 300-500W power, filtering, and performing vacuum drying to obtain an aerogel-glass fiber three-dimensional interpenetrating inorganic skeleton unit; (2) The preparation of the component A comprises the steps of adding flame-retardant aromatic polyether polyol and phthalic anhydride polyester polyol into a reaction kettle, heating to 55-60 ℃ and uniformly stirring, sequentially adding an aerogel-glass fiber three-dimensional interpenetrating inorganic skeleton unit, a composite flame retardant, a composite silicone oil stabilizer and a composite catalyst, stirring at constant temperature of 55-65 ℃ and 750-850 rpm for 55-65 min, cooling to below 30 ℃, adding an environment-friendly foaming agent and deionized water, hermetically stirring, and vacuum defoaming to obtain uniform component A feed liquid, wherein the temperature of the component A feed liquid is 25+/-2 ℃ and the viscosity of the component A feed liquid is 3000-5000 Pa s; (3) High-pressure foaming and in-mold curing, namely high-pressure mixing the feed liquid of the component A and the polymeric MDI of the component B through a high-pressure foaming machine, injecting the mixture into a mold preheated to 45-50 ℃ according to a set injection amount, closing the mold, and performing in-mold heat preservation, pressure maintaining foaming and curing; (4) And (3) post-treatment and finished product processing, namely demolding the plate after in-mold curing, sending the plate into a constant-temperature drying room for secondary curing, and then cutting edges and polishing to obtain the pre-composite aerogel modified polyurethane foaming insulation board.
  9. 9. The preparation method of the pre-composite aerogel modified polyurethane foam insulation board is characterized in that in the step (3), the injection pressure of the high-pressure foaming machine is 15-20 MPa, the mixing pressure is 22-25 MPa, the foaming and curing time is 15-20 min, the injection quantity is calculated according to a formula of 'mold volume multiplied by target apparent density multiplied by 1.05 filling coefficient', and the target apparent density is 110-120 kg/m < 3 >.
  10. 10. The preparation method of the pre-composite aerogel modified polyurethane foam insulation board according to claim 8, wherein in the step (4), the temperature of the secondary curing is 60-65 ℃ and the time is 3-6 hours.

Description

Pre-composite aerogel modified polyurethane foam insulation board and preparation method thereof Technical Field The application relates to a pre-composite aerogel modified polyurethane foaming insulation board and a preparation method thereof, and belongs to the technical field of polyurethane insulation materials. Background Rigid polyurethane foam is widely applied to the fields of building external wall insulation, cold chain logistics, industrial pipelines and the like due to the excellent closed cell structure and extremely low heat conductivity coefficient. However, polyurethane materials are inherently flammable and release a lot of heat and toxic fumes when burned. With the increasingly strict national requirements on the fireproof safety of buildings, the traditional B1 or B2-grade polyurethane heat insulation material has difficulty in meeting the requirements of high-end buildings and special industrial fields on A-grade nonflammable materials. Currently, the conventional method for improving the flame retardant property of polyurethane is to add a large amount of inorganic flame retardant (such as aluminum hydroxide, ammonium polyphosphate, etc.) or to use a halogen-containing flame retardant. However, excessive addition of the inorganic flame retardant seriously damages the cell structure of polyurethane, so that the closed porosity is reduced, the heat conductivity coefficient is greatly increased, the compressive strength is greatly reduced, the water absorption rate is increased, and the halogen-containing flame retardant generates extremely toxic and corrosive gas during combustion and does not meet the environmental protection requirement. In addition, in order to reduce the heat conductivity coefficient, the introduction of silica aerogel is attempted in the industry, but the aerogel is extremely easy to agglomerate and difficult to uniformly disperse in polyurethane resin, and the nano porous structure of the silica aerogel is easy to absorb oil and water, so that the viscosity of a foaming system is suddenly increased and the foaming process is out of control. The Chinese patent CN 121594245A discloses a nano aerogel modified polyurethane heat-insulating pipe and a preparation method thereof, and particularly discloses a heat-insulating pipe which sequentially comprises a working pipe, a modified polyurethane heat-insulating layer and an outer protective pipe from inside to outside, wherein the modified polyurethane heat-insulating layer is formed by compounding and foaming polyol composite materials, isocyanate and nano aerogel, nano aerogel is introduced into the patent, the heat conductivity coefficient is reduced to a certain extent, but a flame retardant system is conventional, flame retardant performance, heat-insulating performance and mechanical performance cannot be considered, the Chinese patent CN 121375267A discloses a polyurethane composite heat-insulating board with good flame retardant effect, and particularly discloses a polyurethane composite heat-insulating board which comprises a fireproof surface layer pretreatment, a flame-retardant core layer preparation, an enhanced substrate layer treatment, lamination molding and post-treatment. However, the lamination composite technology is adopted, the defects of easy delamination of an interlayer interface and poor long-term weather resistance exist, the flame-retardant system of the core layer is still a conventional phosphorus-nitrogen system, and the flame-retardant durability is insufficient. Therefore, how to stably improve the flame retardant property to A2 level without sacrificing the excellent heat preservation property and mechanical strength of polyurethane, solve the difficult problems of aerogel dispersion, fiber reinforcement and foaming system adaptation, realize the multi-performance synergistic balance of 'low heat conduction, high flame retardance, high strength, low water absorption and long durability', and become a major technical bottleneck to be broken through in the field of the current polyurethane heat preservation materials. Disclosure of Invention In order to solve the problems, the pre-composite aerogel modified polyurethane foaming insulation board and the preparation method thereof are provided, wherein the three-dimensional interpenetrating inorganic framework is formed by the cooperation of modified silica aerogel powder and modified glass fiber through pre-composite, a polyol system and polymeric MDI are cooperated, and the comprehensive performance of the insulation board is obviously improved through high-pressure foaming and in-mold curing molding, so that the cooperative balance of the insulation performance, the flame retardant performance and the mechanical performance is realized. According to one aspect of the application, the pre-composite aerogel modified polyurethane foaming insulation board is prepared by high-pressure foaming and in-mold curing of a component A and a component