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CN-121975186-A - Low-toxicity environment-friendly modified melamine cyanurate flame retardant and preparation method and application thereof

CN121975186ACN 121975186 ACN121975186 ACN 121975186ACN-121975186-A

Abstract

The invention provides a low-toxicity environment-friendly modified melamine cyanurate flame retardant and a preparation method and application thereof, and belongs to the technical field of flame retardants. The preparation method comprises the steps of mixing melamine, cyanuric acid, a complexing agent, cardanol and water to obtain slurry, reacting the slurry and drying, and mixing modified melamine cyanurate, a heat stabilizer, a modifier and a silane coupling agent to obtain the modified melamine cyanurate flame retardant. The thiazole group-containing compound and the oxygen-containing intermediate generated by thermal oxidative degradation of the high polymer and the intermediate containing unsaturated bonds generate macromolecules such as sulfur-containing and nitrogen-containing heterocycles, so that the charcoal formation is promoted, a compact protective layer is formed on the surface of the material, the flame retardant property of the material is improved, the pi-pi conjugation effect is formed by the unsaturated hydroxyl group in cardanol and melamine cyanurate, the interface combination of MCA and the polymer is enhanced, and the flame retardant property, the mechanical property and the ageing resistance of the polymer material are improved.

Inventors

  • HU JING
  • GUO ANPENG
  • WANG XINLIANG
  • LIU BINGYANG
  • HAN WEIHUA
  • YUAN JINXIU
  • ZHANG YINGCHAO

Assignees

  • 潍坊科技学院
  • 山东东信新材料科技股份有限公司

Dates

Publication Date
20260505
Application Date
20260129

Claims (10)

  1. 1. The preparation method of the low-toxicity environment-friendly modified melamine cyanurate flame retardant is characterized by comprising the following steps of: 1) Mixing melamine, cyanuric acid, a complexing agent, cardanol and water to obtain slurry, and drying after the slurry reacts to obtain modified melamine cyanurate, wherein the complexing agent is a compound containing thiazole groups; 2) And mixing the modified melamine cyanurate, the heat stabilizer, the modifier and the silane coupling agent to obtain the modified melamine cyanurate flame retardant.
  2. 2. The preparation method according to claim 1, wherein the molar ratio of the melamine to the cyanuric acid in the step 1) is 1:1-1.3, the mass-volume ratio of the sum of the melamine and the cyanuric acid to the cardanol is 0.07-0.11 g:1mL, and the mass of the complexing agent is 0.5-3% of the sum of the melamine and the cyanuric acid.
  3. 3. The preparation method according to claim 1 or 2, wherein the mixing temperature in step 1) is 50-70 ℃, the mixing time is 3-5 h, the mixing mode is ball milling, and the ball-material ratio is 15-20:1.
  4. 4. The preparation method according to claim 3, wherein the reaction temperature in step 1) is 90-130 ℃, the reaction time is 3-5 hours, the reaction is performed under a protective gas, the flow rate of the protective gas is 80-100 mL/min, stirring is performed during the reaction, the stirring speed is 100-150 rpm, the drying temperature is 80-110 ℃, and the drying time is 1-3 hours.
  5. 5. The method according to claim 4, wherein the thiazole group-containing compound of step 1) contains one or more of 2-mercaptothiazoline, 2-mercaptobenzothiazole zinc salt, 2- (4-morpholinyldithio) benzothiazole and dibenzothiazyl disulfide.
  6. 6. The preparation method according to claim 4 or 5, wherein the mass ratio of the modified melamine cyanurate, the heat stabilizer, the modifier and the silane coupling agent in the step 2) is 65-75:6-10:2-5:4-8.
  7. 7. The preparation method according to claim 6, wherein the heat stabilizer in the step 2) is magnesium hydroxide and/or aluminum hydroxide, and the modifier comprises one or more of diatomite, wollastonite and boron nitride.
  8. 8. The method according to claim 7, wherein the mixing temperature in step 2) is 70-90 ℃, the mixing time is 3-5 hours, and the mixing mode is ball milling.
  9. 9. The low-toxicity environment-friendly modified melamine cyanurate flame retardant prepared by the preparation method of any one of claims 1-8.
  10. 10. The use of the low toxicity, environmentally friendly modified melamine cyanurate flame retardant of claim 9 in nylon, ethylene vinyl acetate, polyester and polyolefin.

Description

Low-toxicity environment-friendly modified melamine cyanurate flame retardant and preparation method and application thereof Technical Field The invention relates to the technical field of flame retardants, in particular to a low-toxicity environment-friendly modified melamine cyanurate flame retardant, and a preparation method and application thereof. Background Compared with halogen-containing and phosphorus-containing flame retardants, the melamine flame retardant has great advantages in environmental protection. As a nitrogen halogen-free flame retardant, the flame retardant avoids the harm of strong toxicity and large smoke quantity, solves the defect of poor heat stability of the phosphorus flame retardant, and has the advantages of low price, strong applicability, high flame retardant efficiency and the like. Melamine cyanurate is taken as a halogen-free flame retardant to be widely applied to the industry of polyamide engineering plastics, and is an important nitrogen flame retardant. Melamine Cyanurate (MCA) is a macromolecular complex with a layered structure generated by the reaction of Melamine (MEL) and Cyanuric Acid (CA), and the MCA has the advantages of high efficiency, no halogen, no toxicity, low smoke and the like, and can be used for various polymers, especially flame retardants of nylon high polymer materials. MCA is very stable below 300 ℃,350 ℃ sublimates but does not decompose, and MCA has high nitrogen content, is dehydrated to form charcoal at high temperature, emits nitrogen gas during combustion, can dilute the concentration of oxygen and combustible gas around the combustion environment, and does not generate toxic gas, thus being a flame retardant with excellent performance. MCA has been widely used in flame retardation of nylon-type polymer materials. However, MCA has a high melting point, so that the MCA and nylon are often solid-phase particles when blended, and are unevenly dispersed, thereby affecting the flame-retardant effect. Because the MCA is mainly gas-phase flame retardant, the carbon forming amount on the surface of the polymer is low and the carbon layer is loose in the combustion process, a compact protective layer cannot be formed, and the flame retardant efficiency of the MCA is reduced. The modified melamine cyanurate flame retardant is used in a polymer, has poor compatibility and is easy to cause the reduction of flame retardant effect and mechanical property, and the flame retardant performance, mechanical property and stability of the polymer cannot be improved at the same time. Therefore, the low-toxicity environment-friendly modified melamine cyanurate flame retardant with excellent flame retardant property, mechanical property and good stability and the preparation method thereof are provided, and the low-toxicity environment-friendly modified melamine cyanurate flame retardant has important significance. Disclosure of Invention The invention aims to provide a low-toxicity environment-friendly modified melamine cyanurate flame retardant and a preparation method and application thereof, aiming at overcoming the defects of the prior art. In order to achieve the above object, the present invention provides the following technical solutions: the invention provides a preparation method of a low-toxicity environment-friendly modified melamine cyanurate flame retardant, which comprises the following steps: 1) Mixing melamine, cyanuric acid, a complexing agent, cardanol and water to obtain slurry, and drying after the slurry reacts to obtain modified melamine cyanurate, wherein the complexing agent is a compound containing thiazole groups; 2) And mixing the modified melamine cyanurate, the heat stabilizer, the modifier and the silane coupling agent to obtain the modified melamine cyanurate flame retardant. Preferably, the mole ratio of the melamine to the cyanuric acid in the step 1) is 1:1-1.3, the mass and volume ratio of the sum of the melamine and the cyanuric acid to the cardanol is 0.07-0.11 g:1mL, and the mass of the complexing agent is 0.5-3% of the sum of the melamine and the cyanuric acid. Preferably, the temperature of the mixing in the step 1) is 50-70 ℃, the mixing time is 3-5 h, the mixing mode is ball milling, and the ball-to-material ratio is 15-20:1. Preferably, the temperature of the reaction in the step 1) is 90-130 ℃, the reaction time is 3-5 h, the reaction is carried out under the protection gas, the flow rate of the protection gas is 80-100 mL/min, the stirring speed is 100-150 rpm in the reaction process, the drying temperature is 80-110 ℃, and the drying time is 1-3 h. Preferably, the compound containing thiazole groups in the step 1) comprises one or more of 2-mercaptothiazoline, 2-mercaptobenzothiazole zinc salt, 2- (4-morpholinyldithio) benzothiazole and dibenzothiazyl disulfide. Preferably, in the step 2), the mass ratio of the modified melamine cyanurate, the heat stabilizer, the modifier and the silane coupling agent is 65-75:6-10