CN-120737323-B - Flame-retardant anti-dripping polyester material and preparation method thereof

Abstract

The invention relates to the field of flame-retardant materials, and particularly discloses a flame-retardant anti-dripping polyester material and a preparation method thereof, wherein the preparation method of the polyester material comprises esterification reaction and polycondensation reaction, the molecular structure of the polyester is designed by introducing a copolymerization unit in the esterification stage, the formation of carbon in the heating process is promoted, the carbon residue is enhanced, the release of volatile products is reduced, and the molten drop phenomenon is inhibited, so that the high-performance polyester material with flame retardance, anti-drop property and excellent mechanical property is obtained, and the defects of poor compatibility with a polymer matrix, unsatisfactory flame retardance durability, mechanical property loss and the like of the additive flame retardant are overcome.

Inventors

• SHEN XIANGYU
• Gou Jiaomin
• DONG CHONG
• LI GUANGCHAO
• CHEN JIALEI
• LI BO
• ZHAO ZHEN
• WANG YANG

Assignees

• 河南源宏高分子新材料有限公司

Dates

Publication Date

20260512

Application Date

20250626

Claims (6)

1. 1. The preparation method of the flame-retardant anti-dripping polyester material is characterized by comprising the following steps of: S1, carrying out esterification reaction, namely mixing dibasic acid with a modified monomer to obtain mixed acid, mixing dihydric alcohol with the modified monomer to obtain mixed alcohol, stirring the mixed acid, the mixed alcohol and an esterification catalyst under the condition of 0.1-0.3 MPa or normal pressure at 200-220 ℃, when the water to be removed reaches more than 80% of a theoretical value, raising the temperature to 230-260 ℃ and continuously stirring, and stopping stirring when the water to be removed reaches 95% of the theoretical value; S2, performing polycondensation reaction, namely decompressing to normal pressure, adding a polycondensation catalyst, controlling the reaction temperature to be 270-285 ℃, decompressing to 10-100 Pa, extracting byproduct micromolecular dihydric alcohol and oligomer, filling nitrogen to return to normal pressure after no byproduct is removed, obtaining a polymer melt, and granulating the polymer melt by introducing materials to obtain the viscosity flame-retardant anti-dripping polyester material; The modified monomer comprises at least one of bisphenol A, bisphenol F, dihydroxybiphenyl, diphenyl ether dicarboxylic acid and biphenyl dicarboxylic acid; The dibasic acid comprises terephthalic acid and sodium terephthalate; the dihydric alcohol comprises ethylene glycol and neopentyl glycol; The polycondensation catalyst is a compound of antimony compound, titanium compound and germanium compound.
2. 2. The method for preparing a flame-retardant and anti-dripping polyester material according to claim 1, wherein in the step S1, the average molar ratio of the mixed acid to the mixed alcohol is 1 (1.2-1.7).
3. 3. The method for preparing a flame-retardant and anti-dripping polyester material according to claim 1, wherein in the step S1, the mole ratio of the modifying monomer in the mixed acid is 0-10%.
4. 4. The preparation method of the flame-retardant anti-dripping polyester material according to claim 1, wherein in the step S1, the mole ratio of the dihydric alcohol in the mixed alcohol is 85-95% and the mole ratio of the modifying monomer is 5-15% based on 100% by mole.
5. 5. The method for preparing a flame retardant and anti-dripping polyester material according to claim 1, wherein in the step S1, the esterification catalyst is a complex of a zinc compound, a manganese compound and a tin compound.
6. 6. A flame retardant anti-drip polyester material obtained by the preparation method according to any one of claims 1 to 5, characterized in that the limiting oxygen index of the flame retardant anti-drip polyester material is >30%.

Description

Flame-retardant anti-dripping polyester material and preparation method thereof Technical Field The invention belongs to the field of flame-retardant materials, and particularly relates to a flame-retardant anti-dripping polyester material and a preparation method thereof. Background The polyester material is widely applied to the fields of packaging, construction, household appliances and the like, the cracking temperature is generally 420-450 ℃, and the ignition point of the volatile component is about 480 ℃, so that the polyester material has inflammability, and when the ignition phenomenon occurs, the heat release rate of the polyester is very fast, and the maximum heat release time is less than 15 seconds. At present, with the development of safety consciousness of people, the development of functionalization and differentiation of products, the flame retardance and the flame resistance of polyester materials are widely concerned, the addition of flame retardants is a main technical scheme for improving the flame retardance of the materials at present, but high-efficiency flame retardants, particularly halogen flame retardants, such as decabromodiphenyl ether, decabromodiphenyl ether and the like, can generate toxic gas after thermal decomposition and cause great harm to human bodies and the environment, and in addition, the filling and use of a large amount of flame retardants can also influence the mechanical properties of the materials, such as triphenyl phosphate, melamine and the like, which are phosphorus-containing flame retardants, play a certain plasticizing role on the polyester, reduce the temperature tolerance of the materials, and the toughness of the polyester is reduced to a certain extent, so that the materials become brittle. Meanwhile, most of phosphorus-containing copolyester can drip in fire, secondary injury and scald are caused to human bodies, and high-temperature melt produced by polymer burning dripping falls to ignite other objects to burn, which is also one of main reasons for fire spread. Aiming at the combustion and dripping phenomenon of polyurethane, patent application CN102888012A discloses a method for preparing anti-dripping flame-retardant polyester by radiation crosslinking, wherein polyester chips are mixed with a radiation sensitizer and a flame retardant, extrusion granulation and processing molding are carried out, and the obtained section is crosslinked by electron beam or gamma ray radiation, so that the anti-dripping flame-retardant polyester with flame retardant property and anti-dripping effect is prepared. Patent application CN102534855B discloses a preparation method of durable halogen-free flame-retardant anti-dripping polyester fiber, which comprises the steps of irradiating a primary durable flame-retardant polyester fiber on a high-energy electron accelerator with the irradiation dose of 60-200 kGy, so that the durable halogen-free flame-retardant anti-dripping polyester fiber is obtained, does not generate melt dripping during combustion, can effectively resist dripping, and does not release toxic hydrogen halide gas and smoke. Patent application CN101580976B discloses a preparation method of anti-dripping flame-retardant polyester fiber, which comprises the steps of mixing anti-dripping agent with polyester chips, melt spinning, and then sequentially carrying out alkaline solution treatment, acidic solution treatment and post-treatment to obtain the anti-dripping flame-retardant polyester fiber. From the above patent application, the main stream of the method for relieving the anti-dripping phenomenon of the material combustion is to add a cross-linking agent and an anti-dripping agent, wherein the cross-linking is an effective method for promoting the char formation, the char formation on the surface of an object is increased in the combustion process, and the melt dripping can be effectively prevented, and the anti-dripping agent widely used at present is polytetrafluoroethylene, and the melt strength is increased in the combustion process, so that the dripping is prevented. However, the additive is easy to agglomerate and has poor dispersibility in the use process, and the additive also has a certain influence on the mechanical properties of the material. Disclosure of Invention In order to overcome the defects in the prior art, the invention designs the molecular structure by introducing the copolymerization unit in the esterification stage, promotes the formation of carbon in the heating process, enhances the carbon residue, reduces the release of volatile products and inhibits the phenomenon of molten drops, thereby obtaining the high-performance polyester material with flame retardance, drip prevention and excellent mechanical property, and solving the defects of poor compatibility with a polymer matrix, unsatisfactory flame retardance durability, mechanical property loss and the like of the additive flame retardant. In order to achieve the ab