CN-122011736-A - Reinforced aerogel modified polyurethane foaming insulation board and preparation method thereof

CN122011736ACN 122011736 ACN122011736 ACN 122011736ACN-122011736-A

Abstract

The application discloses a reinforced aerogel modified polyurethane foaming insulation board and a preparation method thereof, and belongs to the technical field of polyurethane insulation flame-retardant materials. The reinforced aerogel modified polyurethane foaming insulation board is prepared by foaming, curing and forming a component A and a component B, wherein the component A comprises, by weight, 100 parts of polyol, 6-15 parts of modified silica aerogel, 8-18 parts of modified glass fibers, 20-35 parts of hybrid ceramic composite flame retardants, 4-8 parts of foaming agents, 0.5-1.5 parts of water, 1.0-2.0 parts of silicone oil foam stabilizers and 0.5-1.5 parts of composite catalysts, and the component B is polyphenyl polymethylene polyisocyanate, and the mass ratio of the component B to the component A is (0.8-1.0): 1. By adopting the modified silica aerogel, the modified glass fiber and the hybrid ceramic composite flame retardant and matching with the proportion of A, B components, the heat conductivity coefficient is obviously reduced, the excellent heat insulation performance is maintained, the mechanical strength of the plate is enhanced, a ceramic barrier can be formed at high temperature, and the synergistic improvement of ultralow heat conduction, high strength and high-grade flame retardant performance is realized.

Inventors

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

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: 20260323

Claims (10)

1. The reinforced aerogel modified polyurethane foaming insulation board is characterized by being prepared by foaming, curing and forming a component A and a component B, wherein the component A comprises, by weight, 100 parts of polyol, 6-15 parts of modified silica aerogel, 8-18 parts of modified glass fiber, 20-35 parts of hybrid ceramic composite flame retardant, 4-8 parts of foaming agent, 0.5-1.5 parts of water, 1.0-2.0 parts of silicone oil foam stabilizer and 0.5-1.5 parts of composite catalyst, and the component B is polyphenyl polymethylene polyisocyanate, and the mass ratio of the component B to the component A is (0.8-1.0): 1.
2. The reinforced aerogel modified polyurethane foam insulation board of claim 1, wherein the polyol is a polyether polyol and a polyester polyol, and/or The hybrid ceramic composite flame retardant comprises liquid polyborosilazane and hexa- (4-hydroxymethyl phenoxy) cyclotriphosphazene, wherein the mass ratio of the liquid polyborosilazane to the hexa- (4-hydroxymethyl phenoxy) cyclotriphosphazene is (2-4): 1.
3. The reinforced aerogel modified polyurethane foam insulation board of claim 1, wherein the modified silica aerogel is a cage polysilsesquioxane shielding modified silica aerogel, and the modified glass fiber is a ZnO nanowire-flexible polyether modified glass fiber.
4. The reinforced aerogel modified polyurethane foam insulation board of claim 3, wherein the cage polysilsesquioxane shielding modified silica aerogel is prepared by the steps of: Dispersing the hydrophobic silica aerogel in absolute ethyl alcohol, adding octa (gamma-isocyanatopropyl) cage-type silsesquioxane and a dibutyl tin dilaurate catalyst, refluxing for 4-6 hours at 60-75 ℃ under the protection of nitrogen, centrifugally washing and vacuum drying to obtain the cage-type polysilsesquioxane shielding modified silica aerogel.
5. The reinforced aerogel modified polyurethane foam insulation board of claim 4, wherein the addition amount of the octa (gamma-isocyanatopropyl) cage-type silsesquioxane is 10-20% of the mass of the hydrophobic silica aerogel.
6. The reinforced aerogel modified polyurethane foam insulation board of claim 3, wherein the ZnO nanowire-flexible polyether modified glass fiber is prepared by the following steps: Soaking alkali-free chopped glass fibers in a dopamine hydrochloride solution, stirring at normal temperature for 24-36 h to obtain glass fibers coated with a polydopamine coating on the surface, immersing the glass fibers coated with the polydopamine coating on the surface in an aqueous solution containing zinc acetate and hexamethylenetetramine, performing hydrothermal reaction for 6-8 h in a water bath at 85-95 ℃, washing and drying, immersing in an isocyanate-terminated polyether prepolymer solution, and performing reaction for 2.5-3.5 h at 65-75 ℃ to obtain ZnO nanowire-flexible polyether modified glass fibers.
7. The reinforced aerogel modified polyurethane foam insulation board of claim 1, wherein the concentration of the dopamine hydrochloride solution is 1.5-3 g/L, and the solvent of the dopamine hydrochloride solution is Tris-HCl buffer solution with pH=8.5-10.
8. The reinforced aerogel modified polyurethane foam insulation board disclosed by claim 1 is characterized in that the polyol consists of flame-retardant aromatic polyether polyol and aromatic polyester polyol according to a mass ratio of 7:3-8:2, the foaming agent is prepared by compounding cyclopentane and 1-chloro-3, 3-trifluoropropene according to a mass ratio of 1:1-1:2, the silicone oil foam stabilizer is a polyether modified polysiloxane foam stabilizer, and the composite catalyst consists of N, N-dimethyl cyclohexylamine and 1,3, 5-tris (dimethylaminopropyl) hexahydro-s-triazine according to a mass ratio of 1:1.5-1:2.5.
9. The method for preparing the reinforced aerogel modified polyurethane foam insulation board as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps: (1) Pre-dispersing, namely taking the raw materials in parts by weight, sequentially adding the hybrid ceramic composite flame retardant and the modified silica aerogel into the polyol, and uniformly dispersing to obtain a dispersion liquid; (2) Constructing a three-dimensional framework, namely adding modified glass fibers into the dispersion liquid, and stirring and mixing to obtain a component A premix; (3) Curing and foaming, namely sequentially adding water, a foaming agent, a stabilizer and a composite catalyst into the premix of the component A, uniformly stirring, adding the component B, mixing at a high speed, and rapidly injecting into a die; (4) Curing and curing, namely curing and molding for 22-28 hours at the constant temperature of 45-60 ℃, and demolding and cutting to obtain the reinforced aerogel modified polyurethane foaming insulation board.
10. The preparation method of the reinforced aerogel modified polyurethane foaming insulation board is characterized in that the uniform dispersion in the step (1) is carried out by adopting a high-shear emulsifying machine, the rotating speed is 3000-5000 r/min, the time is 15-20 min, the stirring and mixing in the step (2) are carried out by adopting a planetary stirrer, the stirring rotating speed is 50-100 r/min, the stirring time is 25-35 min, and the high-speed mixing rotating speed in the step (3) is 1500-2000 r/min, and the time is 6-10 s.

Description

Reinforced aerogel modified polyurethane foaming insulation board and preparation method thereof Technical Field The application relates to a reinforced aerogel modified polyurethane foaming insulation board and a preparation method thereof, belonging to the technical field of polyurethane insulation flame-retardant materials. Background Polyurethane (PU) rigid foam material plays an irreplaceable role in the fields of building energy conservation, cold chain logistics, special equipment heat preservation and the like by virtue of the extremely low heat conductivity coefficient, the excellent closed cell structure and the good construction performance. With the increasing strictness of building fireproof standards, the development of polyurethane heat-insulating boards with ultra-low heat conductivity and high-grade flame retardant performance (grade A or quasi-grade A) has become the core direction of industry development. At present, in the prior art, by introducing aerogel filler with a nano-pore structure into a foaming system, the gas convection in cells can be effectively inhibited, and fiber materials can compensate matrix embrittlement caused by the large-quantity addition of filler, so that an attempt is made to construct a high-performance composite system. However, in existing modification practices, the thermal insulation efficacy of aerogels is often difficult to achieve perfect release in polyurethane systems, the core reason of which is interference from capillary siphon effects. The existing silica aerogel surface treatment mostly depends on a silane coupling agent or a simple surface hydrophobizing means, and the modification of the two-dimensional scale is difficult to construct an effective physical barrier at an aerogel nanoscale aperture opening. In the initial stage of the polyurethane foaming reaction, the viscosity of the system is low, and isocyanate or polyol monomers with extremely strong penetrability inevitably penetrate into the aerogel particles through capillary action and occupy the nano-pores originally used for blocking heat during the subsequent curing process. The pore filling phenomenon not only directly leads the thermal conductivity coefficient of the composite material to rebound greatly, so that the initial purpose of reducing the thermal conductivity is lost due to the introduction of aerogel, but also serious waste of expensive raw materials is caused, and the aerogel becomes a 'fatal injury' which restricts the large-scale application of the aerogel in the field of heat preservation. On the other hand, the traditional reinforcing and flame-retardant modifying means bring remarkable mechanical weakening and potential safety hazard to the plate while improving the performance. In the prior art, the treatment of the glass fiber as the reinforcing filler is often limited to chemical grafting or plasma etching, and the surface morphology of the fiber is lack of deep three-dimensional modification, so that the mechanical anchoring force between the fiber and the wall of the polyurethane foam hole is insufficient, and the fiber is extremely easy to undergo interfacial debonding when subjected to impact or compression test. More serious, the so-called high-performance flame-retardant polyurethane board which is currently marketed depends on the addition of a large amount of traditional powder flame retardants such as ammonium polyphosphate, aluminum hydroxide or melamine. The expansion carbon layer formed by the flame retardants when encountering high-temperature fire sources is extremely loose and low in physical strength, and is extremely easy to break and fall off under the violent impact of flame airflow, so that a fire penetration phenomenon is generated, and the mechanical strength of the plate is also reduced. In summary, the existing polyurethane insulation board modification technology shows obvious synergistic failure characteristics when facing multiple requirements of extreme insulation, high toughness and extreme fire safety. How to meet the multiple requirements of the polyurethane heat-insulating board on heat-insulating performance, mechanical performance and flame-retardant performance, and realize the balance among the heat-insulating performance, the mechanical performance and the flame-retardant performance, so that the comprehensive improvement of the material performance is a key scientific problem which needs to be solved in the field of the current polyurethane heat-insulating materials. Disclosure of Invention In order to solve the problems, the application provides the reinforced aerogel modified polyurethane foaming insulation board and the preparation method thereof, and the modified silica aerogel, the modified glass fiber and the hybridized ceramic composite flame retardant are adopted to match the proportion of A, B components, so that the blocking of the pores of the aerogel by isocyanate and polyol is effectively avoided, the heat conduct