CN-119752160-B - Flame-retardant nylon material and preparation method thereof

Abstract

The invention discloses a halogen-free flame-retardant nylon material, which comprises PA, a toughening agent, a P-series flame retardant, an N-series flame retardant, modified polyhedral oligomeric silsesquioxane and a flame-retardant synergist of derivatives thereof. The modified polyhedral oligomeric silsesquioxane and the derivative flame-retardant synergist thereof contain boron elements, a ring-shaped structure R 2 with the hydrocarbon ratio being more than 1 and 2 inorganic silicon cage cores, and the structures form a carbon layer, a ceramic barrier layer, a protective film or a heat-insulating coke layer and other protective layers in the combustion process, so that the anti-dripping effect is greatly improved, meanwhile, heat and oxygen transmission is isolated, the release of combustible gas is reduced, and the flame-retardant performance of the material is remarkably improved under the combined action of multiple mechanisms. Further, the flame-retardant synergist of the modified polyhedral oligomeric silsesquioxane and the derivative thereof is matched with the P-series flame retardant and the N-series flame retardant to realize synergistic flame retardance, so that the flame retardant consumption of the flame retardant is reduced, and the flame retardant performance of the flame-retardant nylon material is improved. The halogen-free flame-retardant nylon material provided by the invention has excellent flame retardant property.

Inventors

• BO QIANGLONG
• Fu Rifei
• WANG YINGJIE
• DONG XIN
• LIU WEIQI
• ZHENG HAIMEI
• XIONG XIKE
• ZHU LIUQING
• LI JINGLIN
• ZHOU DAN

Assignees

• 深圳市沃尔核材股份有限公司

Dates

Publication Date

20260512

Application Date

20241231

Claims (9)

1. 1. The flame-retardant nylon material is characterized by comprising the following raw materials in parts by weight: 50-70 parts of PA (polyamide), 1-5 Parts of a toughening agent, 3-10 Parts of P-series flame retardant, 3-10 Parts of N-series flame retardant, 2-12 Parts of modified polyhedral oligomeric silsesquioxane and a derivative flame retardant synergist thereof, Wherein, the structure of the modified polyhedral oligomeric silsesquioxane and the derivative flame retardant synergist thereof is as follows: Wherein R is isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl or phenyl, R 1 is propylene or phenylene; R 2 is a 2-benzo [ B ] naphtho [2,3-D ] furanyl group, a 3-dibenzofuranyl group; The P-series flame retardant is an inorganic phosphorus flame retardant or an organic phosphorus flame retardant, wherein the inorganic phosphorus flame retardant is at least one of red phosphorus, phosphate and polyphosphate, the organic phosphorus flame retardant is at least one of phosphate, phosphite and phosphine oxide, and the N-series flame retardant is at least one of melamine inorganic acid salt.
2. 2. The flame-retardant nylon material of claim 1, wherein the modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist is prepared by dehydration reaction of a compound 1 and a compound 2 under the action of a catalyst, and the reaction route is as follows: 。
3. 3. the flame retardant nylon material of claim 2, wherein the molar ratio of compound 1 to compound 2 is 2:1.
4. 4. The flame retardant nylon material of claim 2, wherein the preparation method of the modified polyhedral oligomeric silsesquioxane and derivative flame retardant synergist thereof comprises the following steps: dissolving a compound 1 in an organic solvent, adding an aqueous solution of the compound 2 under the action of a catalyst, performing catalytic reaction, and washing and drying to obtain the modified polyhedral oligomeric silsesquioxane and the flame-retardant synergist of the derivative of the polyhedral oligomeric silsesquioxane; Wherein the organic solvent is at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones and glycol derivatives; the catalyst is at least one of an acid catalyst, a metal catalyst and an alkaline catalyst.
5. 5. The flame retardant nylon material of claim 1, wherein the flame retardant nylon material comprises the following raw materials in parts by weight: 50-70 parts of PA (polyamide), 1-5 Parts of a toughening agent, 3-7 Parts of P-series flame retardant, 3-7 Parts of N-series flame retardant, 2-12 Parts of modified polyhedral oligomeric silsesquioxane and a derivative flame retardant synergist thereof.
6. 6. The flame retardant nylon material of claim 1, wherein the toughening agent is at least one of an ethylene-octene copolymer, an ethylene propylene copolymer, EMA, EBA.
7. 7. The flame-retardant nylon material according to claim 1, wherein the raw materials of the flame-retardant nylon material further comprise at least one of a lubricant and an antioxidant, wherein the raw materials comprise, by weight, 0.2-1 part of the lubricant and 0.5-2 parts of the antioxidant.
8. 8. A method for preparing the flame-retardant nylon material according to claim 1, which is characterized by comprising the following steps of uniformly mixing the raw materials, extruding and granulating by an extruder to obtain granules, namely the flame-retardant nylon material.
9. 9. The method for preparing a flame retardant nylon material according to claim 8, wherein the raw materials further comprise at least one of a lubricant and an antioxidant.

Description

Flame-retardant nylon material and preparation method thereof Technical Field The invention relates to the field of materials, in particular to a halogen-free flame-retardant nylon material. Background Polyhedral oligomeric silsesquioxane (polyhedral oligomericsilsesquioxane, POSS for short) is a special organic amorphous material, is a polycyclic organic monomer, consists of silicon frames (siliconframework) and oxygen atoms of embedded bonds of the silicon frames, is an inorganic-organic hybrid nanomaterial, and is an inorganic silicon cage core in the POSS is decomposed by heating to form a compact ceramic barrier layer to isolate the release of combustible gas and the external heat from entering the inside, so that the further decomposition of the material is delayed, and the POSS has great application potential in the field of flame retardants. Nylon (PA) materials belong to a class of polymer materials with stronger polarity, and hydrogen bonds can be formed among molecules, so that the melting temperature is higher, the melting temperature range is narrower, the melting point is obvious, and the nylon (PA) materials are widely applied to various industries, but because the nylon materials have no flame retardant property, the nylon is subjected to flame retardant modification to become a new direction of the nylon materials, and at present, the nylon is subjected to flame retardant modification mainly in two types of chemical modification and physical modification. The chemical flame-retardant modification is to introduce a flame-retardant component into the main chain or side chain of nylon through chemical reaction, so that the molecular chain has flame-retardant property. The physical flame-retardant modification is to introduce a flame-retardant component or a flame retardant into a nylon matrix, and prepare the flame-retardant modified nylon material through mixing and granulating. The blending flame retardant modification is the most convenient and widely used method, and the flame retardant melamine polyphosphate (MPP) is an ideal flame retardant for nylon, has chemical composition elements similar to nylon and has good compatibility with a nylon matrix. Meanwhile, melamine polyphosphate molecules contain nitrogen and phosphorus elements, the flame retardant efficiency is high, alkyl phosphinate, melamine polyphosphate and the like are used as flame retardants, nylon is used as a matrix, and the flame retardant antistatic nylon material is prepared by melt blending through an extruder. Disclosure of Invention In view of the defects in the prior art, the invention provides a halogen-free flame-retardant nylon material, and aims to solve the problem of poor flame retardance of the current PA material. The above object of the present invention is achieved by the following technical solutions: The invention provides a flame-retardant nylon material, which comprises the following raw materials in parts by weight: 50-70 parts of PA (polyamide), 1-5 Parts of a toughening agent, 3-10 Parts of P-series flame retardant, 3-10 Parts of N-series flame retardant, 2-15 Parts of modified polyhedral oligomeric silsesquioxane and a derivative flame retardant synergist thereof, Wherein, the structure of the modified polyhedral oligomeric silsesquioxane and the derivative flame retardant synergist thereof is as follows: wherein R is a non-reactive group, such as isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, phenyl, etc., and R 1 is n-propyl or phenylene; R 2 is a cyclic structure with a hydrocarbon ratio of more than 1, and comprises at least one of a benzofuran group and a polycyclic aromatic group. In some embodiments of the invention, the benzofuran groups include at least one of benzofuran groups, dibenzofuran groups; and/or the polycyclic aromatic group includes at least one of a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, an acenaphthylene ring group, a fluorene ring group, and a perylene ring group. In some embodiments of the present invention, the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is prepared by dehydration reaction of a compound 1 and a compound 2 under the action of a catalyst, and the reaction route is as follows: In some embodiments of the invention, the molar ratio of compound 1 to compound 2 is 2:1. In some embodiments of the present invention, the method for preparing the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist comprises the following steps: dissolving a compound 1 in an organic solvent, adding an aqueous solution of the compound 2 under the action of a catalyst, performing catalytic reaction, and washing and drying to obtain the modified polyhedral oligomeric silsesquioxane and the flame-retardant synergist of the derivative of the polyhedral oligomeric silsesquioxane; wherein the organic solvent comprises at least one of alcohols, aromatic hydrocarbons