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CN-122011441-A - Long glass fiber reinforced polyurethane composite material and preparation process and application thereof

CN122011441ACN 122011441 ACN122011441 ACN 122011441ACN-122011441-A

Abstract

The invention discloses a long glass fiber reinforced polyurethane composite material and a preparation process and application thereof, wherein a calcium ion doped zirconium-based MOF is adopted and modified by phosphonite to form a P-Br reaction layer, and partial zirconium-hydroxyl coordination sites are replaced by doped calcium ions to form a non-catalytic metal center, so that the coupling and cyclization reaction tendency of aromatic halides in the combustion process of a bromination system is weakened, bromine free radicals in a gas phase can be efficiently captured by the material in the combustion process, and a P-H bond in the phosphonite group and the bromine free radicals are utilized to carry out rapid chemical reaction to generate a stable P-Br structure, thereby preventing the bromine free radicals from participating in generating toxic substances such as hydrogen bromide or brominated dioxin, remarkably reducing the release amount of toxic smoke and corrosive gas in the combustion process, further improving the safety of the composite material in a fire scene, and enabling the composite material to meet the strict standard of low smoke and low toxicity of building materials, and effectively guaranteeing the safety of escape personnel and rescue.

Inventors

  • SHAO HONGTAO
  • WANG WEI
  • SHAO MINGCHEN

Assignees

  • 万仑新材料(上海)有限公司

Dates

Publication Date
20260512
Application Date
20260313

Claims (10)

  1. 1. The preparation process of the long glass fiber reinforced polyurethane composite material is characterized by comprising the following steps of: Step S1, performing solvothermal reaction on a zirconium source and a solvent system of an organic ligand, and adding alkaline earth metal salt solution containing calcium ions to obtain calcium ion doped zirconium-based MOF; s2, dispersing the zirconium-based MOF in ethanol, adding a phosphonite group for modification, and forming a P-Br reaction layer chemically combined with bromine free radicals on the surface layer to obtain a modified zirconium-based MOF; step S3, uniformly mixing the long glass fiber, polyurethane, a bromine flame retardant and the modified zirconium-based MOF master batch obtained in the step S2 in a high-shear mixer to obtain a mixture; s4, continuously drawing and solidifying the mixture at a die temperature of 45-70 ℃ through a pultrusion process to obtain a long glass fiber reinforced polyurethane composite section; And S5, performing post-curing on the composite profile for 1.5-3 hours at the temperature of 80-100 ℃ to enable zirconium-based MOF to be enriched in a region with the outer edge of 100-300 mu m of the profile to form functional gradient distribution.
  2. 2. The process for preparing a long glass fiber reinforced polyurethane composite material according to claim 1, wherein in the step S1, zirconium source is zirconium tetrachloride, organic ligand is terephthalic acid, solvent is N, N-dimethylformamide, alkaline earth metal salt solution containing calcium ions is calcium nitrate tetrahydrate; In the solvothermal reaction, glacial acetic acid is required to be added for regulation, wherein the ratio of zirconium tetrachloride to terephthalic acid to glacial acetic acid to water is 1:1-1.5:20-60:6-12.
  3. 3. The preparation process of the long glass fiber reinforced polyurethane composite material according to claim 1, wherein in the step S1, calcium ions are doped relative to Zr in a molar ratio of 0.3-1.5 mol%, the reaction temperature is 120-150 ℃, and the reaction time is 8-24 hours, so that the calcium ion doped zirconium-based MOF is obtained.
  4. 4. The preparation process of the long glass fiber reinforced polyurethane composite material according to claim 1, wherein in the step S2, the silane coupling agent containing the phosphonite group is diethyl phosphonopropyl triethoxysilane, the addition amount is 5-30wt% of the mass of zirconium-based MOF, the reaction is carried out in an ethanol solvent in the presence of a catalyst, the reaction temperature is 35-60 ℃, and the reaction time is 12-24 hours.
  5. 5. The preparation process of the long glass fiber reinforced polyurethane composite material according to claim 1, wherein in the step S2, the modified zirconium-based MOF is washed and dried at 45-60 ℃ for 6-12 hours in vacuum, and then activated at 100-120 ℃ for 4-8 hours in vacuum, so as to remove residual solvent and stabilize the surface layer P-Br reaction layer.
  6. 6. The preparation process of the long glass fiber reinforced polyurethane composite material according to claim 1, wherein in the step S3, the long glass fiber reinforced polyurethane composite material is characterized by comprising the following components in parts by weight: 20-40 parts of long glass fiber; 30-50 parts of polyurethane resin; 5-15 parts of bromine flame retardant; 1-10 parts of modified zirconium-based MOF master batch.
  7. 7. The process for preparing the long glass fiber reinforced polyurethane composite material of claim 6, wherein the bromine flame retardant is at least one of brominated polystyrene and brominated epoxy resin; the length of the long glass fiber is 10-50 mm.
  8. 8. The process for preparing a long glass fiber reinforced polyurethane composite material according to claim 1, wherein in the step S4, the die temperature of the pultrusion process is 45-70 ℃, and the traction speed is 0.2-1.0 m/min.
  9. 9. A long glass fiber reinforced polyurethane composite material, characterized in that the long glass fiber reinforced polyurethane composite material is prepared based on the preparation process of the long glass fiber reinforced polyurethane composite material as claimed in any one of claims 1 to 8.
  10. 10. Use of a long glass fiber reinforced polyurethane composite material obtained by the preparation process of the long glass fiber reinforced polyurethane composite material according to any one of claims 1 to 8 in building doors and windows.

Description

Long glass fiber reinforced polyurethane composite material and preparation process and application thereof Technical Field The invention relates to preparation of a composite material, in particular to a long glass fiber reinforced polyurethane composite material, and a preparation process and application thereof. Background The long glass fiber reinforced polyurethane composite material needs to be added with flame retardants, such as bromine-containing flame retardants, the brominated flame retardants can quickly release bromine free radicals with strong chain termination capability after being heated, and the bromine free radicals directly act on a flame zone, so that a combustion chain reaction is restrained in a very short time, thereby effectively restraining the flame spreading speed, reducing the heat release rate and reducing the continuous thermal shock of flame to a door and window structure, and meanwhile, the long glass fiber reinforced system endows the material with excellent bearing capability and dimensional stability, so that the long glass fiber reinforced system can bear building loads at the positions of door and window frames, stressed side beams and the like, can provide rapid fire-retarding protection at the initial stage of a fire disaster, and can more meet the strict requirements of building on early flame inhibition, stable structure and flame diffusion avoidance compared with a halogen-free flame retardant system relying on later expansion. During combustion, the brominated compounds decompose and release bromine radicals (Br.) to capture high energy H.and HO.radicals in the combustion chain reaction, thereby interrupting combustion. This is a "sacrificial" chemical process, usually accompanied by the generation of a large amount of smoke and potentially toxic gases, in a fire, the main cause of casualties is often inhalation of toxic smoke rather than direct burning, but in a real fire scenario, the bromine flame retardant material may release highly toxic and corrosive gases such as high concentration hydrogen bromide, brominated dioxin, brominated furan, etc., threatening personnel life safety and fire rescue, and in early and late stages of the fire, the temperature may be low, incomplete combustion chemical generation, when bromine-containing organic matters are incompletely combusted at low temperature (200-450 ℃), oxygen and metal ions (such as copper, commonly in electric wires) are extremely easy to generate brominated dioxins and brominated furans through "Ullmann reaction" and "cyclization reaction" under catalysis of oxygen and metal ions. Therefore, it is necessary to design a preparation method of a long glass fiber reinforced polyurethane composite material, which needs to retain the gas phase flame-retarding advantage of brominated flame retardance and solve the problem that other gases and toxic gases are generated during combustion. Disclosure of Invention The invention overcomes the defects of the prior art and provides a long glass fiber reinforced polyurethane composite material and a preparation process and application thereof. In order to achieve the aim, the technical scheme adopted by the invention is that the preparation process of the long glass fiber reinforced polyurethane composite material comprises the following steps: Step S1, performing solvothermal reaction on a zirconium source and a solvent system of an organic ligand, and adding alkaline earth metal salt solution containing calcium ions to obtain calcium ion doped zirconium-based MOF; s2, dispersing the zirconium-based MOF in ethanol, adding a phosphonite group for modification, and forming a P-Br reaction layer chemically combined with bromine free radicals on the surface layer to obtain a modified zirconium-based MOF; step S3, uniformly mixing the long glass fiber, polyurethane, a bromine flame retardant and the modified zirconium-based MOF master batch obtained in the step S2 in a high-shear mixer to obtain a mixture; s4, continuously drawing and solidifying the mixture at a die temperature of 45-70 ℃ through a pultrusion process to obtain a long glass fiber reinforced polyurethane composite section; And S5, performing post-curing on the composite profile for 1.5-3 hours at the temperature of 80-100 ℃ to enable zirconium-based MOF to be enriched in a region with the outer edge of 100-300 mu m of the profile to form functional gradient distribution. In a preferred embodiment of the present invention, in the step S1, the zirconium source is zirconium tetrachloride, the organic ligand is terephthalic acid, the solvent is N, N-dimethylformamide, and the alkaline earth metal salt solution containing calcium ions is calcium nitrate tetrahydrate; In the solvothermal reaction, glacial acetic acid is required to be added for regulation, wherein the ratio of zirconium tetrachloride to terephthalic acid to glacial acetic acid to water is 1:1-1.5:20-60:6-12. In a preferred embodiment of the present