Search

CN-121975278-A - Antibacterial flame-retardant packaging box material and preparation method thereof

CN121975278ACN 121975278 ACN121975278 ACN 121975278ACN-121975278-A

Abstract

The invention discloses an antibacterial flame-retardant packaging box material and a preparation method thereof, relating to the technical field of polyester degradable plastics, the recycled polyethylene glycol terephthalate alcoholysis product and the PBAT resin are blended as a base material, and the product is prepared by melt mixing, phosphorus-nitrogen-phosphorus synergistic flame retardant modification, antibacterial modification and extrusion molding sequentially. The material realizes strong antibacterial effect by synergizing the benzimidazole-containing flame-retardant monomer with 2-carboxyethyl phenyl phosphinic acid and matching with guanidine compounds, has excellent mechanical property and degradability, realizes recycling of waste PET (polyethylene terephthalate) resources, has no toxic residues, meets the requirements of fire prevention, antibacterial effect, environmental protection and processing of a packaging box, and has wide application prospect.

Inventors

  • WANG CHEN

Assignees

  • 南京鑫瑞包装有限公司

Dates

Publication Date
20260505
Application Date
20260302

Claims (10)

  1. 1. S1, adding a polyester alcoholysis product and PBAT resin into a reaction container, and heating, melting and mixing under nitrogen atmosphere to obtain a polyester substrate melting system; S2, sequentially adding benzimidazole-containing flame-retardant monomer, 2-carboxyethyl phenyl phosphinic acid and catalyst into a polyester substrate melting system, heating, and stirring in vacuum to obtain flame-retardant modified polyester; and S3, adding guanidine compounds into the flame-retardant modified polyester, melting and mixing uniformly, extruding, forming and cooling to obtain the antibacterial flame-retardant packaging box material.
  2. 2. The method for preparing the antibacterial flame-retardant packaging box material according to claim 1, wherein the mass ratio of the polyester alcoholysis product to the PBAT resin is (40-60); In the preparation process of the flame-retardant modified polyester, the mass ratio of a polyester substrate melting system, namely a benzimidazole-containing flame-retardant monomer, namely 2-carboxyethyl phenyl phosphinic acid and a catalyst, is 100 (2-5), 1-3 and 0.1-0.5; In the preparation process of the antibacterial flame-retardant modified polyester, the mass ratio of the flame-retardant modified polyester to the guanidine compound is 100 (1-4).
  3. 3. The method for preparing the antibacterial flame-retardant packaging box material according to claim 1, which is characterized by comprising the following steps of adding waste polyethylene terephthalate, 1, 4-butanediol and zinc acetate dihydrate into a reaction container, heating to 195-200 ℃ under nitrogen atmosphere, stirring uniformly, further heating to 225-230 ℃ for reacting for 2-2.5h, dissolving the product by using boiling water, filtering while the product is hot, placing the filtrate in an environment of 0-5 ℃ for cooling crystallization, filtering, and vacuum drying at 60-65 ℃ to obtain the polyester alcoholysis product.
  4. 4. The method for preparing the antibacterial flame-retardant packaging box material according to claim 3, wherein in the preparation process of the polyester alcoholysis product, the molar ratio of the waste polyethylene terephthalate to the 1, 4-butanediol is 1 (1.5-1.6), and the addition amount of the zinc acetate dihydrate is 0.4-0.6% of the mass of the waste polyethylene terephthalate.
  5. 5. The method for preparing the antibacterial flame-retardant packaging box material according to claim 1, which is characterized by comprising the steps of adding 3, 4-diaminobenzoic acid and 2-carboxyethyl phenyl phosphinic acid into 3-3.5mol/L hydrochloric acid solution, heating to 100-105 ℃ for reflux reaction for 8-8.5h, filtering, adjusting the pH of filtrate to 5.8-6.2 by using 25-28wt% ammonia water, washing the precipitated product by using deionized water, vacuum drying at 60-65 ℃ to obtain a powder product, adding the powder product into methanol, adding concentrated sulfuric acid, heating to 80-85 ℃ for reflux reaction for 12-12.5h, spin-evaporating, adding deionized water, adjusting the pH of the precipitated product to 5.8-6.2 by using 25-28wt% ammonia water, washing the precipitated product by using methanol, and vacuum drying at 80-85 ℃ to obtain the benzimidazole-containing flame-retardant packaging box material.
  6. 6. The method for preparing an antibacterial flame-retardant packaging box material according to claim 5, wherein the mass ratio of 3, 4-diaminobenzoic acid to 2-carboxyethyl phenyl phosphinic acid in the preparation process of the powder product is (30.4-31.2) (42.8-45.6).
  7. 7. The method for preparing the antibacterial flame-retardant packaging box material according to claim 1, wherein the method for preparing the guanidine compound comprises the following steps: Adding a mercapto guanidine compound and a double bond ester compound into acetonitrile, adding triethylamine, stirring at room temperature for 3-4h, distilling under reduced pressure, dissolving residues by using ethyl acetate, purifying, eluting, adding a product into a mixed solution of dichloromethane and trifluoroacetic acid in a volume ratio of 1:1, stirring at room temperature for 2-3h, distilling under reduced pressure, and washing by using diethyl ether to obtain the guanidine compound; In the preparation process of the guanidine compound, the molar ratio of the mercapto guanidine compound to the double bond-containing ester compound to the triethylamine is 0.77:0.85:2.3.
  8. 8. The method for preparing the antibacterial flame-retardant packaging box material according to claim 7, wherein the preparation method of the mercapto guanidine compound comprises the following steps of adding 2-mercaptoethylamine hydrochloride and 1, 3-di-BOC-2- (trifluoromethylsulfonyl) guanidine into methylene dichloride, adding triethylamine, reacting for 2-3 hours at room temperature, purifying, eluting to obtain the mercapto guanidine compound; in the preparation process of the mercapto guanidine compound, the molar ratio of the 2-mercaptoethylamine hydrochloride to the 1, 3-di-BOC-2- (trifluoromethyl sulfonyl) guanidine to the triethylamine is 6.7:6.4:14.8.
  9. 9. The method for preparing the antibacterial flame-retardant packaging box material according to claim 7, which is characterized by comprising the following steps of adding 2-methoxyethanol and triethylamine into methylene dichloride under ice bath condition, adding methacryloyl chloride, stirring at room temperature for 3-4h, purifying, and eluting to obtain the double bond-containing ester compound; In the preparation process of the double bond-containing ester compound, the molar ratio of the 2-methoxyethanol to the triethylamine to the methacryloyl chloride is 0.12:0.12:0.059.
  10. 10. An antibacterial flame-retardant packaging box material prepared by the preparation method of the antibacterial flame-retardant packaging box material according to any one of claims 1-9.

Description

Antibacterial flame-retardant packaging box material and preparation method thereof Technical Field The invention relates to the technical field of polyester degradable plastics, in particular to an antibacterial flame-retardant packaging box material and a preparation method thereof. Background The conventional plastic packaging box material has the defects of poor flame retardance and antibacterial property, easy loss caused by fire hidden danger or bacterial pollution in logistics storage, poor mechanical property, poor flame retardance and antibacterial function, difficulty in considering bearing requirements and safety protection, low recycling rate of waste polyester materials, resource waste and environmental pressure. The existing modification technology has the advantages of improving the multi-focusing single function or realizing the function through high-addition-amount additives, so that the processability of the material is reduced, the additives are easy to migrate, and the degradability or the mechanical balance is often sacrificed. In addition, the partial modification process is complex, the energy consumption is high, the risk of toxic solvent residue exists, and the safety and environmental protection requirements of food packaging, logistics transportation and other scenes cannot be met. Therefore, developing a packaging box material with high-efficiency flame retardance, strong-efficiency antibacterial property, green degradability, excellent mechanical property and resource recycling property becomes a problem to be solved urgently in the industry. Disclosure of Invention The invention aims to provide an antibacterial flame-retardant packaging box material and a preparation method thereof, which are used for solving the problems in the prior art. In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the antibacterial flame-retardant packaging box material comprises the following steps: s1, adding a polyester alcoholysis product and PBAT resin into a reaction vessel, and heating, melting and mixing under a nitrogen atmosphere to obtain a polyester substrate melting system; S2, sequentially adding benzimidazole-containing flame-retardant monomer, 2-carboxyethyl phenyl phosphinic acid and catalyst into a polyester substrate melting system, heating, and stirring in vacuum to obtain flame-retardant modified polyester; and S3, adding guanidine compounds into the flame-retardant modified polyester, melting and mixing uniformly, extruding, forming and cooling to obtain the antibacterial flame-retardant packaging box material. Further, in the preparation process of the polyester substrate melting system, the mass ratio of the polyester alcoholysis product to the PBAT resin is (40-60); Further, in the preparation process of the flame-retardant modified polyester, the mass ratio of a polyester substrate melting system, namely benzimidazole-containing flame-retardant monomer, namely 2-carboxyethyl phenyl phosphinic acid and catalyst, is 100 (2-5) (1-3) (0.1-0.5); Further, in the preparation process of the antibacterial flame-retardant modified polyester, the mass ratio of the flame-retardant modified polyester to the guanidine compound is 100 (1-4). Further, the catalyst is prepared by mixing tetrabutyl titanate and ethylene glycol antimony according to a molar ratio of 1:1; Further, the cross-linking agent is 3, 6-dioxa-1, 8-octanedithiol; Further, in the extrusion molding process, the processing temperature is 230-250 ℃, and the extrusion pressure is 60-80MPa; Further, the preparation method of the polyester alcoholysis product comprises the following steps of adding waste polyethylene terephthalate, 1, 4-butanediol and zinc acetate dihydrate into a reaction vessel, heating to 195-200 ℃ under nitrogen atmosphere, stirring uniformly, further heating to 225-230 ℃ to react for 2-2.5h, dissolving the product by using boiling water, filtering while the product is hot, placing the filtrate in an environment of 0-5 ℃ to cool and crystallize, filtering, and vacuum drying at 60-65 ℃ to obtain the polyester alcoholysis product; Further, in the preparation process of the polyester alcoholysis product, the molar ratio of the waste polyethylene terephthalate to the 1, 4-butanediol is 1 (1.5-1.6), and the addition amount of the zinc acetate dihydrate is 0.4-0.6% of the mass of the waste polyethylene terephthalate; The preparation method of the benzimidazole-containing flame-retardant monomer comprises the following steps of adding 3, 4-diaminobenzoic acid and 2-carboxyethyl phenyl phosphinic acid into 3-3.5mol/L hydrochloric acid solution, heating to 100-105 ℃ for reflux reaction for 8-8.5h, filtering, using 25-28wt% ammonia water to adjust the pH of filtrate to 5.8-6.2, washing a precipitated product with deionized water, and vacuum drying at 60-65 ℃ to obtain a powder product; Further, in the preparation process of the powder prod