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CN-121974950-A - Hydrazide phosphorus-nitrogen synergistic reaction type flame retardant, and preparation method and application thereof

CN121974950ACN 121974950 ACN121974950 ACN 121974950ACN-121974950-A

Abstract

The invention belongs to the technical field of flame retardants, and discloses a hydrazino phosphorus nitrogen synergistic reaction type flame retardant, a preparation method and application thereof, wherein R 1 and R 2 in the structural formula of the hydrazino phosphorus nitrogen synergistic reaction type flame retardant are respectively and independently selected from methyl, ethyl or phenyl, R 3 is p-phenyl group, m-phenyl group or (CH 2 ) y ;R 4 is p-phenyl group, m-phenyl group or (CH 2 ) m ), the preparation method is to carry out amidation reaction on dihydrazide and an organophosphorus compound and then polycondensation, so as to prepare the hydrazino phosphorus nitrogen synergistic reaction type flame retardant, and the application is to mix the hydrazino phosphorus nitrogen synergistic reaction type flame retardant, terephthalic acid, ethylene glycol and a catalyst II and then sequentially carry out esterification reaction and polycondensation reaction, so that hydrophilic flame retardant polyester is prepared.

Inventors

  • JI PENG
  • NI QINGTING
  • LIU JIZHE
  • XU CHAOCHEN
  • WANG HUAPING

Assignees

  • 东华大学

Dates

Publication Date
20260505
Application Date
20260407

Claims (10)

  1. 1. The hydrazino phosphorus nitrogen synergistic reaction type flame retardant is characterized by having the structural formula: ; Wherein x=5 to 10, n=0 to 5, R 1 and R 2 are each independently selected from methyl, ethyl or phenyl, R 3 is p-phenyl, m-phenyl or (CH 2 ) y ,y=1~4;R 4 is p-phenyl, m-phenyl or (CH 2 ) m , m=0 to 3).
  2. 2. The method for preparing a hydrazino phosphazene synergistic reaction type flame retardant according to claim 1, wherein dihydrazide and an organic phosphorus compound are subjected to amidation reaction and then polycondensation, so that the hydrazino phosphazene synergistic reaction type flame retardant is prepared.
  3. 3. The method for preparing the hydrazide phosphorus nitrogen synergistic reaction type flame retardant according to claim 2, which is characterized by comprising the following specific preparation steps: (1) Mixing a dihydrazide compound aqueous solution, a catalyst I and an organic phosphorus compound, and then heating to 160-180 ℃ in a normal pressure nitrogen environment at a heating rate of 1-5 ℃ per minute for pre-reaction for 1-1.5 h; (2) Heating the reaction system in the step (1) to 180-200 ℃ at a heating rate of 1-5 ℃ per minute to perform amidation reaction until the reaction water yield reaches 90% of a theoretical value, and performing polycondensation reaction for 1-2 hours at a vacuum degree of 50-100 Pa and a temperature of 190-210 ℃ to obtain the hydrazinophosphorus-nitrogen synergistic reaction type flame retardant.
  4. 4. The preparation method of the hydrazinophosphazene synergistic reaction type flame retardant according to claim 3, which is characterized in that the organophosphorus compound is more than one of phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester and phenylphosphonic acid dimethyl ester, the dihydrazide compound is more than one of terephthalic acid dihydrazide, isophthalic acid dihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide and adipic acid dihydrazide, and the catalyst I is more than one of dibutyl tin dilaurate, tetrabutyl titanate, antimonous oxide, antimony acetate, ethylene glycol antimon and 1, 8-diazabicyclo undec-7-ene.
  5. 5. The method for preparing the hydrazino phosphorus nitrogen synergistic reaction type flame retardant according to claim 3, wherein the mass ratio of water to dihydrazide compound in the dihydrazide compound aqueous solution is 5-10:1, the molar ratio of dihydrazide compound to organophosphorus compound is 1.05-1.35:1, and the content of the catalyst I is 300-1000 ppm.
  6. 6. A method for preparing hydrophilic flame-retardant polyester is characterized in that the hydrazide phosphorus nitrogen synergistic reaction type flame retardant, terephthalic acid, ethylene glycol and a catalyst II are mixed and then sequentially subjected to esterification reaction and polycondensation reaction, so that the hydrophilic flame-retardant polyester is prepared.
  7. 7. The preparation method of the hydrophilic flame-retardant polyester is characterized by comprising the steps of mixing a hydrazide phosphorus nitrogen synergistic reaction type flame retardant, terephthalic acid, ethylene glycol and a catalyst II, carrying out esterification reaction for 1-2 hours at 225-235 ℃ under the protection of nitrogen, and carrying out polycondensation reaction for 2.5-4.5 hours at 265-275 ℃ under the vacuum degree of 50-100 Pa, so as to obtain the hydrophilic flame-retardant polyester.
  8. 8. The preparation method of the hydrophilic flame-retardant polyester is characterized in that the molar ratio of terephthalic acid, ethylene glycol and hydrazono phosphorus nitrogen synergistic reaction type flame retardant is 50:52.5-67.5:1-5, and the content of a catalyst II in the hydrophilic flame-retardant polyester is 300-1000 ppm.
  9. 9. The method for preparing the hydrophilic flame-retardant polyester according to claim 8, wherein the catalyst II is more than one of tetrabutyl titanate, antimony trioxide, antimony acetate, dibutyl tin dilaurate and ethylene glycol antimony.
  10. 10. The method for preparing the hydrophilic flame-retardant polyester according to any one of claims 6 to 9, wherein the limiting oxygen index of the hydrophilic flame-retardant polyester is 30 to 36%, the vertical burning grade UL-94 is V-0, the tensile strength is 35 to 42mpa, the elongation at break is 20 to 40%, and the water contact angle is 35 to 60 °.

Description

Hydrazide phosphorus-nitrogen synergistic reaction type flame retardant, and preparation method and application thereof Technical Field The invention belongs to the technical field of flame retardants, and relates to a hydrazino phosphorus nitrogen synergistic reaction type flame retardant, and a preparation method and application thereof. Background Polyethylene terephthalate (PET) is a typical polyester material obtained by Polycondensation of Terephthalic Acid (PTA) and Ethylene Glycol (EG), and is widely used in the fields of fibers, films, packaging bottles, electronic appliances, and the like because of its characteristics such as non-toxicity, good weather resistance, and good stability. However, the Limiting Oxygen Index (LOI) of the PET material is only 21% -22%, and the PET material belongs to a flammable material, and can cause serious potential safety hazards when burned in air, so that the flame retardant modification research of the PET material has urgency and importance. Currently, flame retardant modification of PET is mainly dependent on physical blending of additive flame retardants or copolymerization modification of reactive flame retardants. The additive flame retardant (such as phosphorus, nitrogen, phosphorus-nitrogen synergistic) is introduced through a melt blending process, for example, the flame retardant is blended with polyester in the patent application with the application publication number of CN120289799A, CN119462765A, but the flame retardance can be improved, the problems of uneven dispersion, easy migration and precipitation and the like of the flame retardant exist, the additive amount is required to be greatly improved in order to achieve the ideal flame retardance grade, the mechanical properties (such as strength and toughness) of the PET matrix are often obviously reduced, and the application of the PET matrix in high-precision structural members is limited. The copolymerization modification can impart more durable flame retardancy to the material by chemically bonding the reactive flame retardant into the PET molecular chain than physical blending. However, existing co-modification techniques still face multiple bottlenecks. The phosphorus-nitrogen synergistic reaction type polyester flame retardant is prepared in the patent application with the application publication number of CN105541917B, CN120904428A and is introduced into polyester through a copolymerization modification method. However, the method can realize flame retardance and durability, simultaneously degrade mechanical properties, and a large amount of toxic organic solvents are applied in the preparation process of the flame retardant, so that the method is not beneficial to industrial production, increases production cost, brings potential safety hazard and causes huge environmental pressure. In addition, the copolymerization modified flame retardant is a reactive flame retardant, most of the flame retardants are of a hydrophobic structure, so that the hydrophilicity of PET can be reduced, and the application of the flame retardant in the fields requiring hydrophilicity and comfort such as spinning, medical treatment and the like is limited. Although the prior art has tried to combine flame retardance and hydrophilicity (such as CN103483573B is copolymerized with a flame retardant structure by introducing hydrophilic groups), the flame retardant group (containing P-O bond) and the hydrophilic groups (such as polyethylene glycol and sulfonate) have large chemical property difference, are easy to generate phase separation or functional interference, lead to the reduction of comprehensive performance, and do not effectively solve the negative influence of the flame retardant on the mechanical property of the polyester. In addition, phosphorus elements in the existing reactive flame retardant exist in a P-O bond mode, the flame retardant efficiency of a single phosphorus-containing component is low, and the application of the reactive flame retardant in a high-temperature processing scene is limited by the high-temperature instability of the P-O bond. Therefore, research on a hydrazide phosphorus nitrogen synergistic reaction type flame retardant, and a preparation method and application thereof are of great significance in solving the problems. Disclosure of Invention The invention aims to solve the problems in the prior art and provides a hydrazidophosphorus-nitrogen synergistic reaction type flame retardant, and a preparation method and application thereof. In order to achieve the above purpose, the invention adopts the following technical scheme: a hydrazino phosphorus nitrogen synergistic reaction type flame retardant has a structural formula: ; Wherein x=5 to 10, n=0 to 5, R 1 and R 2 are each independently selected from methyl, ethyl or phenyl, R 3 is p-phenyl, m-phenyl or (CH 2)y,y=1~4;R4 is p-phenyl, m-phenyl or (CH 2)m, m=0 to 3). The invention also provides a preparation method of the hydrazid