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CN-121975130-A - Reactive flame-retardant antibacterial auxiliary agent for polyester, and preparation method and application thereof

CN121975130ACN 121975130 ACN121975130 ACN 121975130ACN-121975130-A

Abstract

The invention belongs to the technical field of flame retardance and antibiosis, and discloses a reactive flame retardance and antibiosis auxiliary agent for polyester, and a preparation method and application thereof, wherein n=5-10 in a structural formula of the reactive flame retardance and antibiosis auxiliary agent for polyester, R 1 is guanidino or (CH 2 ) y ,y=0,3,4;R 3 is guanidino or (CH 2 ) 0 ;R 2 is methyl, ethyl or phenyl), the preparation method comprises the steps of sequentially carrying out amidation reaction and polycondensation reaction on guanidine compounds and organophosphorus compounds to obtain the reactive flame retardance and antibiosis auxiliary agent for polyester, and the application comprises the steps of carrying out esterification reaction after mixing terephthalic acid, ethylene glycol and a catalyst B, and then adding the reactive flame retardance and antibiosis auxiliary agent for polyester to carry out polycondensation to obtain the flame retardance and antibiosis PET copolyester.

Inventors

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

Assignees

  • 东华大学

Dates

Publication Date
20260505
Application Date
20260407

Claims (11)

  1. 1. A reactive flame-retardant antibacterial auxiliary for polyester is characterized by comprising the following structural formula: ; Wherein n=5 to 10, r 1 is guanidino or (CH 2 ) y ,y=0,3,4;R 3 is guanidino or (CH 2 ) 0 ;R 2 is methyl, ethyl or phenyl).
  2. 2. The method for preparing a reactive flame-retardant and antibacterial auxiliary for polyesters according to claim 1, wherein the guanidine compound and the organophosphorus compound are subjected to amidation reaction and polycondensation reaction in sequence, thereby preparing the reactive flame-retardant and antibacterial auxiliary for polyesters.
  3. 3. The preparation method of the reactive flame-retardant antibacterial auxiliary for polyester is characterized by comprising the specific steps of mixing guanidine compounds, organic phosphorus compounds and catalysts A, reacting for 2-3 hours at 160-180 ℃ under the protection of nitrogen, and then reacting for 1-2 hours at 195-225 ℃ under the vacuum degree of 50-100 Pa, so as to obtain the reactive flame-retardant antibacterial auxiliary for polyester.
  4. 4. The method for preparing a reactive flame-retardant antibacterial auxiliary for polyesters according to claim 2, wherein the organophosphorus compound is one or more of phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, dimethyl methylphosphonate, dimethyl ethylphosphonate and dimethyl phenylphosphonate, and the guanidine compound is one or more of guanidine, biguanidine, aminoguanidine, 1, 3-diaminoguanidine, agmatine and polyurethane biguanidine.
  5. 5. The method for preparing a reactive flame-retardant antibacterial auxiliary for polyesters according to claim 2, wherein the molar ratio of guanidine compounds to organic phosphorus compounds is 2.05-2.35:1.
  6. 6. The method for preparing the reactive flame-retardant and antibacterial auxiliary for polyesters according to claim 3, wherein the catalyst A is one or more of anhydrous sodium acetate, anhydrous zinc acetate, zinc oxide, dibutyl tin dilaurate, tetrabutyl titanate, antimony trioxide, antimony acetate, ethylene glycol antimony and 1, 8-diazabicyclo undec-7-ene, and the content of the catalyst A in the reactive flame-retardant and antibacterial auxiliary for polyesters is 300-1000 ppm.
  7. 7. The application of the reactive flame-retardant and antibacterial auxiliary for polyester for preparing flame-retardant and antibacterial PET copolyester is characterized in that after terephthalic acid, ethylene glycol and a catalyst B are mixed, esterification reaction is carried out, and then the reactive flame-retardant and antibacterial auxiliary for polyester as claimed in claim 1 is added for polycondensation, so that the flame-retardant and antibacterial PET copolyester is prepared.
  8. 8. The application of the reactive flame-retardant and antibacterial auxiliary for polyester, which is disclosed in claim 7, is characterized in that the specific preparation method comprises the steps of mixing terephthalic acid, ethylene glycol and a catalyst B, carrying out esterification reaction for 2-3 hours at 225-235 ℃ under the protection of nitrogen, adding the reactive flame-retardant and antibacterial auxiliary for polyester, 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 flame-retardant and antibacterial PET copolyester.
  9. 9. The application of the reactive flame-retardant and antibacterial auxiliary for polyester according to claim 7, wherein the molar ratio of terephthalic acid to ethylene glycol to the reactive flame-retardant and antibacterial auxiliary for polyester is 50:52.5-67.5:1-5, and the addition amount of the catalyst B in the flame-retardant and antibacterial PET copolyester is 300-1000 ppm.
  10. 10. The application of the reactive flame-retardant antibacterial auxiliary for polyesters according to claim 9, wherein the catalyst B is one or more of tetrabutyl titanate, antimony trioxide, antimony acetate, ethylene glycol antimony and dibutyltin dilaurate.
  11. 11. The use of a reactive flame-retardant and antibacterial auxiliary for polyesters according to any one of claims 7 to 10, characterized in that the limiting oxygen index of the flame-retardant and antibacterial PET copolyester is 31 to 37%, the vertical burning rating UL-94 is V-0, the tensile strength is 35 to 42mpa, the elongation at break is 5 to 20%, and the antibacterial rate meets the AAA-level standard.

Description

Reactive flame-retardant antibacterial auxiliary agent for polyester, and preparation method and application thereof Technical Field The invention belongs to the technical field of flame retardance and antibiosis, and relates to a reactive flame retardance and antibiosis auxiliary agent for polyester, and a preparation method and application thereof. Background Polyethylene terephthalate (PET) is almost ubiquitous in everyday life. PET is valued for its excellent characteristics of non-toxicity, weather resistance, stability, etc., and is suitable for the fields of fiber, sheet, packaging, automobile parts, etc. When a fire disaster occurs, common clothes can burn, melt and adhere to skin rapidly when meeting fire, and serious or deadly burn is caused. And the firefighter can sweat in a large amount during firefighting operation when the firefighter is directly exposed to open fire and high-temperature heat radiation, so that a high-temperature, high-humidity and closed microenvironment is formed in the protective clothing, bacteria are easy to breed, and the application range of the polyester fiber material is limited. Therefore, it is important to perform flame retardant and antibacterial modification on PET polyester materials. The cationic antibacterial polyester chips and the flame-retardant polyester chips prepared by the polymerization reaction are subjected to the double-component composite spinning to prepare the antibacterial flame-retardant polyester fiber with the sheath-core structure in the patent application with the application publication number of CN 119685972A. The flame-retardant component of the core layer in the skin-core structure cannot exert the flame-inhibiting function in time when a fire disaster occurs, and can exert the flame-retardant performance after the antibacterial skin layer burns and the flame-retardant core layer is exposed, so that the flame-retardant efficiency of the flame-retardant antibacterial polyester is reduced. In the patent with the publication number of CN117646290B, quaternized glycol, terephthalic acid, TEOS and titanium catalyst are fully mixed, and then the low molecular weight flame-retardant antibacterial hydrophobic copolyester is prepared through esterification reaction and sol-gel reaction, and the flame-retardant antibacterial polyester industrial yarn is prepared by blending yarn with high molecular weight polyester. The flame-retardant antibacterial agent is introduced into the polyester matrix by a blending method, so that the problems of uneven dispersion, poor durability and reduced mechanical property are easily caused while the functional modification is realized, and the quaternized diol in the flame-retardant antibacterial agent contains halogen element Br, so that toxic gas is easily released in the combustion process to cause environmental pollution, and the flame-retardant antibacterial agent is not beneficial to industrial production. In summary, since the chemical properties of the flame retardant group and the antibacterial group may be greatly different, simple physical mixing may generate phase separation or mutual interference, and when copolymerization of multiple functional monomers is involved, precise control of monomer feed ratio and reaction conditions is required to ensure that the functional groups are introduced into polymer molecule segments according to design proportion to realize repeatability and processing stability, and in addition, the introduction of functional monomers changes the chemical structure of the material, which may adversely affect mechanical properties or other original properties of the material, and balance between functionalization and maintaining basic properties of the substrate is required. Therefore, the development of the environment-friendly reactive flame-retardant antibacterial agent which realizes flame retardance and antibacterial functionalization of polyester and has excellent mechanical properties at the same time has important significance. Disclosure of Invention The invention aims to solve the problems in the prior art and provides a reactive flame-retardant antibacterial auxiliary agent for polyester, and a preparation method and application thereof. In order to achieve the above purpose, the invention adopts the following technical scheme: a reactive flame-retardant antibacterial auxiliary for polyester has the structural formula: ; Wherein n=5 to 10, r 1 is guanidino or (CH 2)y,y=0,3,4;R3 is guanidino or (CH 2)0;R2 is methyl, ethyl or phenyl), and the wavy line means a repeating unit structure with a wavy line: 。 The invention also provides a preparation method of the reactive flame-retardant antibacterial auxiliary for polyester, which comprises the step of sequentially carrying out amidation reaction and polycondensation reaction on guanidine compounds and organophosphorus compounds, so as to obtain the reactive flame-retardant antibacterial auxiliary for polyester. The react