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CN-121974949-A - Silane end-capped reactive phosphate flame retardant, preparation method thereof and application thereof in building exterior wall heat insulation polyurethane

CN121974949ACN 121974949 ACN121974949 ACN 121974949ACN-121974949-A

Abstract

The invention discloses a silane end-capped reactive phosphate flame retardant, a preparation method thereof and application thereof in building external wall heat insulation polyurethane, and belongs to the technical field of high polymer flame retardant materials. The flame retardant has the structure of (RO) 3 Si-Z-NH-COO-[X-NH-COO] n -Y-O-P(=O)(OCH 3 )CH 3 , Z is C2-C6 alkylene, and is coordinated with X is C4-C12 alkylene, n is 1-5, Y is C2-C6 alkylene substituted by hydroxyl, so that good compatibility is achieved, meanwhile, the cohesiveness with building base materials is greatly improved, and a phosphorus flame-retardant source, a long-chain flexible spacer and a hydrolyzable silane end group integrated in a molecular structure are directly involved in polyurethane reaction as a polyol component, so that the flame retardant grade and the heat preservation of foam are greatly improved.

Inventors

  • WANG YONGBIN
  • CHEN BO
  • CHEN GEN
  • CHENG JIAN

Assignees

  • 江苏城乡建设职业学院

Dates

Publication Date
20260505
Application Date
20260128

Claims (10)

  1. 1. A silane end-capped reaction type phosphate flame retardant is characterized by comprising the following structural components: (RO) 3 Si-Z-NH-COO-[X-NH-COO] n -Y-O-P(=O)(OCH 3 )CH 3 Wherein R is selected from C1-C4 alkyl, Z is C2-C6 alkylene, X is C4-C12 alkylene, n is 1 to 5;Y is C2-C6 alkylene, which alkylene is optionally substituted with one or more hydroxyl groups.
  2. 2. The method for preparing a silane end-capped reactive phosphate flame retardant of claim 1, comprising the steps of: S1, in the presence of a catalyst, carrying out ring-opening esterification reaction on dimethyl methylphosphonate and glycidol to obtain a hydroxyl-containing phosphate intermediate, wherein the structural formula is HO-CH 2 CH(OH)CH 2 -O-P(=O)(OCH 3 )CH 3 ; S2, reacting the intermediate obtained in the step S1 with excessive long-chain flexible diisocyanate in the presence of anhydrous and catalyst to generate a prepolymer with isocyanate groups at the tail ends; S3, reacting the prepolymer obtained in the step S2 with amino alkoxy silane to obtain the silane end-capped reaction type phosphate flame retardant.
  3. 3. The method for preparing a silane end-capped reaction type phosphate flame retardant according to claim 2, wherein the catalyst in the step S1 is a tertiary amine, quaternary ammonium salt or phosphine catalyst.
  4. 4. The method for preparing a silane end-capped reaction type phosphate flame retardant according to claim 2, wherein the catalyst in the step S1 is triethylamine, N-dimethylbenzylamine, tetrabutylammonium bromide or triphenylphosphine.
  5. 5. The method for preparing a silane-terminated reactive phosphate flame retardant according to claim 2, wherein the long-chain flexible diisocyanate in the step S2 is hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or decane diisocyanate.
  6. 6. The method for preparing a silane end-capped reaction type phosphate flame retardant according to claim 2, wherein the catalyst in the step S2 is dibutyl tin dilaurate or stannous octoate.
  7. 7. The method for preparing a silane-terminated reactive phosphate flame retardant as claimed in claim 2, wherein the aminoalkoxysilane in the step S3 is aminopropyl triethoxysilane, aminopropyl trimethoxysilane or aminoethylaminopropyl trimethoxysilane.
  8. 8. The method for preparing a silane end-capped reaction type phosphate flame retardant according to claim 2, wherein the reaction temperature in the step 1 is 60-90 ℃, the reaction temperature in the step 2 is 40-70 ℃, and the reaction temperature in the step 3 is 30-60 ℃.
  9. 9. The application of the silane end-capped reactive phosphate flame retardant in the heat-insulating polyurethane for the building outer wall is characterized in that the heat-insulating polyurethane for the building outer wall comprises polyalcohol, water, a catalyst, a foam stabilizer, a foaming agent and isocyanate, wherein the polyalcohol comprises the silane end-capped reactive phosphate flame retardant according to any one of claims 1-8, and the addition amount of the silane end-capped reactive phosphate flame retardant is 10-40% of the mass of the polyalcohol.
  10. 10. The application of the silane end-capped reactive phosphate flame retardant in the heat-insulating polyurethane for the building exterior wall, as claimed in claim 9, is characterized in that the addition amount of the silane end-capped reactive phosphate flame retardant is 30% of the mass of the polyol; And/or, the polyol further comprises a polyether polyol; And/or the mass ratio of the polyol to the isocyanate is 1:1; and/or the isocyanate is polymeric MDI.

Description

Silane end-capped reactive phosphate flame retardant, preparation method thereof and application thereof in building exterior wall heat insulation polyurethane Technical Field The invention belongs to the technical field of high polymer flame retardant materials, and particularly relates to a silane end-capped reactive phosphate flame retardant, a preparation method thereof and application thereof in heat-insulating polyurethane for an external wall of a building. Background Energy-saving heat preservation of building wall is one of the important points of modern building field, and polyurethane rigid foam is widely applied to the building energy-saving field due to excellent heat preservation performance. However, since the conventional polyurethane rigid foam is a polymer material, the oxygen index is only about 17 without adding flame retardant, and the polyurethane rigid foam is extremely easy to burn under normal conditions. At present, flame retardance of polyurethane heat insulation materials in the market is basically improved by adding flame retardants, such as DMMP (dimethyl formamide), tris (2-chloropropyl) phosphate (TCPP for short), so that flame retardance of foams is improved, but the conventional added flame retardants (such as TCPP and DMMP) have the problems of easiness in migration and volatilization, influence on long-term dimensional stability and heat conductivity of the foams, insufficient adhesion force with base materials and the like. Although the reactive flame retardant can solve the migration problem, the flexibility or interfacial adhesion performance of the foam is often damaged, for example, the reactive flame retardant disclosed in Chinese patent document (application number 202010334508.0) has the structural formula ofWherein R is a C1-C18 alkyl chain, m is an integer of 1 or 2, and X is Cl or Br. Therefore, developing a single molecular structure that can simultaneously impart durable flame retardancy, good flexibility, and high adhesion to a substrate to polyurethane foam through chemical bonds is a technical problem to be solved in the art. Disclosure of Invention The invention aims to provide a preparation method of a silane end-capped reaction type phosphate flame retardant, wherein a phosphorus flame retardant source, a long-chain flexible spacer and a hydrolyzable silane end group are integrated in the molecular structure of the prepared flame retardant, and the flame retardant can be used as a polyol component to directly participate in polyurethane reaction, so that the flame retardant has excellent flame retardant property, dimensional stability, heat insulation and heat preservation performance, and high compression strength and bonding strength. The technical scheme adopted for solving the problems is that the preparation method of the silane end-capped reaction type phosphate flame retardant comprises the following steps: S1, in the presence of a catalyst, carrying out ring-opening esterification reaction on dimethyl methylphosphonate and glycidol to obtain a hydroxyl-containing phosphate intermediate A HO-CH 2CH(OH)CH2-O-P(=O)(OCH3)CH3; S2, reacting the intermediate A obtained in the step S1 with excessive long-chain flexible diisocyanate in the presence of anhydrous catalyst to generate a prepolymer B with an isocyanate group at the tail end; S3, reacting the prepolymer B obtained in the step S2 with amino alkoxy silane to obtain the silane end-capped reaction type phosphate flame retardant. Preferably, the catalyst in the step S1 is tertiary amine, quaternary ammonium salt or phosphine catalyst, and the glycidol is 2, 3-epoxy-1-propanol. More preferably, the catalyst is triethylamine, N-dimethylbenzylamine, tetrabutylammonium bromide or triphenylphosphine. Preferably, the long chain flexible diisocyanate in step S2 is hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or decane diisocyanate. Preferably, the catalyst in step S2 is dibutyltin dilaurate or stannous octoate. Preferably, the aminoalkoxysilane in step S3 is aminopropyl triethoxysilane, aminopropyl trimethoxysilane or aminoethylaminopropyl trimethoxysilane. Preferably, the reaction temperature in step 1 is 60-90 ℃, the reaction temperature in step 2 is 40-70 ℃, and the reaction temperature in step 3 is 30-60 ℃. Preferably, in step S2, the long-chain flexible diisocyanate is added in batches to the reaction kettle containing the intermediate a, the dehydrating agent and the catalyst, specifically, half of the amount is slowly added to react for at least 1.5 hours, and then the remaining amount is added dropwise. The invention also aims to provide the silane end-capping reaction type phosphate flame retardant, which is prepared by adopting the preparation method of the silane end-capping reaction type phosphate flame retardant. The structure of the silane end-capped reactive phosphate flame retardant is shown as follows: (RO)3Si-Z-NH-COO-[X-NH-COO]n-Y-O-P(=O)(OCH3)C