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CN-121975220-A - Nano reinforced flame-retardant master batch and application thereof in metal composite plate

CN121975220ACN 121975220 ACN121975220 ACN 121975220ACN-121975220-A

Abstract

The application relates to the technical field of polymer materials, and discloses a nano reinforced flame-retardant master batch and application thereof in metal composite plates, the nano reinforced flame-retardant master batch is prepared from magnesium hydroxide, linear low density polyethylene, a polyolefin elastomer, a maleic anhydride grafted polyolefin elastomer, a hydroxyl-rich B-stage precursor and an auxiliary agent. The hydroxyl-rich B-stage precursor is a prepolymer with secondary hydroxyl formed by epoxy soybean oil and dodecenyl succinic anhydride under the catalysis of nano cerium oxide. The preparation method of the nano reinforced flame-retardant master batch comprises the steps of spraying and anchoring a precursor on the surface of magnesium hydroxide, and then carrying out twin-screw reactive extrusion. The application solves the problems of poor interface combination and difficult processing of a high-filling system by constructing an interface chemical bonding network, endows the material with excellent flame retardance, toughness and processing rheological property, and is suitable for the core material of the metal composite board.

Inventors

  • DU YANG
  • LV YUMIN
  • LV ZHENG
  • LI FEI

Assignees

  • 莱芜华夏瑞特新材料科技有限公司

Dates

Publication Date
20260505
Application Date
20260313

Claims (10)

  1. 1. The nano reinforced flame-retardant master batch is characterized by being prepared from the following raw materials in parts by weight: 80.0-85.0 parts of magnesium hydroxide; 5.0-10.0 parts of linear low-density polyethylene; 3.0-5.0 parts of polyolefin elastomer; 3.0-6.0 parts of maleic anhydride grafted polyolefin elastomer; 1.0-2.5 parts of hydroxyl-rich B-stage precursor; 0.1-1.0 parts of zinc stearate; 0.1-0.5 parts of lubricant; The hydroxyl-rich B-stage precursor is a prepolymer with secondary hydroxyl formed by ring-opening esterification of epoxidized soybean oil and dodecenyl succinic anhydride under the catalysis of nano cerium dioxide.
  2. 2. The nano-reinforced flame-retardant masterbatch according to claim 1, wherein the raw materials consist of the following components in parts by weight: 82.0 parts of magnesium hydroxide; 8.0 parts of linear low density polyethylene; 4.0 parts of polyolefin elastomer; 4.0 parts of maleic anhydride grafted polyolefin elastomer; 1.75 parts of hydroxyl-rich B-stage precursor; 0.4 parts of zinc stearate; 0.2 parts of lubricant; Wherein the lubricant is selected from one or more of pentaerythritol stearate, polyethylene wax and oxidized polyethylene wax.
  3. 3. The nano reinforced flame-retardant master batch according to claim 1, wherein the hydroxyl-rich B-stage precursor is prepared by reacting the following raw materials in parts by weight at 95-105 ℃: 100 parts of epoxidized soybean oil; 30-55 parts of dodecenyl succinic anhydride; 3.0-6.0 parts of nano cerium dioxide.
  4. 4. The nano reinforced flame-retardant master batch according to claim 1, wherein the magnesium hydroxide is prepared by a chemical synthesis method, the median particle diameter d 50 is 1.0-2.0 μm, the specific surface area is 7.0-9.0 m 2 /g, the surface is not subjected to organic modification treatment, and the grafting rate of the maleic anhydride grafted polyolefin elastomer is 0.8-1.2 wt%.
  5. 5. The nano reinforced flame-retardant master batch according to claim 3, wherein the average particle size of the nano cerium oxide is 20-40 nm, and the total amount of rare earth oxide is not less than 99%.
  6. 6. A method for preparing the nano-reinforced flame-retardant masterbatch according to any one of claims 1-5, comprising the steps of: s1, heating and drying magnesium hydroxide, adding a hydroxyl-rich B-stage precursor for mixing through atomization spraying, anchoring the hydroxyl-rich B-stage precursor on the surface of the magnesium hydroxide, then adding zinc stearate for high-speed shearing and mixing, and cooling to obtain modified powder; S2, uniformly mixing the modified powder with linear low density polyethylene, a polyolefin elastomer, a maleic anhydride grafted polyolefin elastomer and a lubricant; s3, feeding the mixed material obtained in the step S2 into a double-screw extruder for reactive extrusion granulation to obtain the nano reinforced flame-retardant master batch.
  7. 7. The method for preparing the nano reinforced flame-retardant master batch according to claim 6, wherein in the step S1, the magnesium hydroxide is heated to 110-115 ℃, the mixing time after spraying the hydroxyl-rich B-stage precursor is 5-8 min, and the high-speed shearing time after adding the zinc stearate is 40-90S.
  8. 8. The method for preparing the nano-reinforced flame-retardant master batch according to claim 6, wherein the preparation steps of the hydroxyl-enriched B-stage precursor are as follows: Mixing and heating the epoxidized soybean oil and dodecenyl succinic anhydride to 55-65 ℃, adding nano cerium dioxide, and shearing and dispersing for 5-12 min at the rotating speed of 1000-160 rpm; Then heating to 95-105 ℃, and reacting for 25-35 min at a constant temperature under the rotation speed of 200-400 rpm until the reaction liquid is dark amber and can be drawn; and cooling to 80 ℃ after the reaction is finished, and preserving heat for later use.
  9. 9. The method for preparing the nano reinforced flame-retardant master batch according to claim 6, wherein in the step S3, the length-diameter ratio L/D of the screws of the double-screw extruder is more than or equal to 44, and continuously arranged toothed disc elements are arranged in a reaction section, wherein the temperature of the reaction section is set to be 190-200 ℃.
  10. 10. Use of the nano-reinforced flame-retardant masterbatch according to any one of claims 1-5 in the preparation of a metal composite board core material.

Description

Nano reinforced flame-retardant master batch and application thereof in metal composite plate Technical Field The invention relates to the technical field of high polymer materials, in particular to a nano reinforced flame-retardant master batch and application thereof in metal composite boards. Background The metal composite board is used as an important building decoration material, and the fire resistance of the integral board is directly determined by the combustion performance of the core material. In order to meet the A2-level fire protection standard, inorganic flame retardants such as magnesium hydroxide with a mass fraction of more than 80% are generally required to be filled in the core material formula. The ultrahigh filling amount can cause the continuous phase of the polymer matrix to be seriously blocked by inorganic particles, so that the melt viscosity is rapidly increased, the processing rheological property is deteriorated, and the surface roughness and even melt fracture easily occur in the extrusion molding process. Meanwhile, because of the huge polarity difference between the inorganic powder and the organic matrix, the interfacial compatibility of the inorganic powder and the organic matrix is poor, so that the mechanical property, particularly the elongation at break and the impact strength of the composite material are greatly reduced, the material shows obvious brittleness, and the requirement of the metal composite board on the flexibility of the core material in the continuous thermal compounding and subsequent rolling and bending processing processes is difficult to meet. The prior art generally uses silane or titanate type small molecule coupling agents to surface treat magnesium hydroxide to improve dispersibility. However, the coverage rate of the modifier on the powder surface is limited, and the modifier is mainly dependent on physical adsorption or weak chemical bonding, so that desorption or failure is easy to occur under the conditions of ultra-high filling and strong shearing processing, and sufficient interface bonding strength cannot be provided. In addition, while increasing the amount of elastomeric toughening agent can improve material brittleness to some extent, this tends to result in reduced flame retardant properties and excessive processing torque. Therefore, how to solve the problems of dispersion stability and interface bonding fastness of inorganic particles in a matrix on the premise of maintaining an ultrahigh filling quantity to ensure flame retardant grade, thereby balancing the flame retardance, mechanical property and processing property of the material is a main technical problem facing the current field. Therefore, the invention provides a nano reinforced flame-retardant master batch and application thereof in metal composite plates, and aims to solve the defects in the prior art. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a nano reinforced flame-retardant master batch and application thereof in a metal composite board, and solves the problems of poor melt fluidity, weak interface binding force between inorganic powder and an organic matrix, reduced mechanical property and difficult processing of the existing high-filling magnesium hydroxide flame-retardant master batch. In order to solve the problems, the invention provides the following technical scheme: in a first aspect, the invention provides a nano-reinforced flame-retardant master batch, which adopts the following technical scheme: The nano reinforced flame-retardant master batch is prepared from the following raw materials, by weight, 80.0-85.0 parts of magnesium hydroxide, 5.0-10.0 parts of linear low-density polyethylene, 3.0-5.0 parts of polyolefin elastomer, 3.0-6.0 parts of maleic anhydride grafted polyolefin elastomer, 1.0-2.5 parts of hydroxyl-rich B-stage precursor, 0.1-1.0 parts of zinc stearate and 0.1-0.5 part of lubricant, wherein the hydroxyl-rich B-stage precursor is a prepolymer with secondary hydroxyl formed by ring-opening esterification of epoxy soybean oil and dodecenyl succinic anhydride under the catalysis of nano cerium dioxide. By adopting the technical scheme, the hydroxyl-rich B-stage precursor is used as the reactive interface modifier, so that the dispersion state and the interface bonding strength of the magnesium hydroxide in the polyolefin matrix are improved. The specific mechanism and effect are as follows: First, interfacial chemical bonding enhancement mechanisms. The hydroxyl-rich B-stage precursor contains a plurality of secondary hydroxyl and ester active sites. In the mixing process, the precursor forms a chemical anchoring layer on the surface of the inorganic particles through hydrogen bond adsorption or condensation reaction between the secondary hydroxyl and the hydroxyl on the surface of the magnesium hydroxide, and in the extrusion processing stage, the residual epoxy groups and hydroxyl of the precursor