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CN-121991315-A - Querc Pi Suji polyurethane material, novel metal-ligand coordination crosslinked polyurethane material, and preparation method and application thereof

CN121991315ACN 121991315 ACN121991315 ACN 121991315ACN-121991315-A

Abstract

The invention provides a quercetin Pi Suji polyurethane material, a novel metal-ligand coordination crosslinked polyurethane material, a preparation method and application thereof, belonging to the technical field of polyurethane materials, wherein the novel metal-ligand coordination crosslinked polyurethane has the following structural formula: the preparation method comprises the steps of adding diisocyanate into a completely melted dihydric alcohol oligomer system, reacting to obtain isocyanate terminated prepolymer, adding quercetin solution into the prepolymer system, reacting to obtain quercetin Pi Suji polyurethane solution, adding metal ion solution into the quercetin Pi Suji polyurethane solution system, and volatilizing a solvent after the reaction to obtain the novel metal-ligand coordination crosslinked polyurethane material. The invention takes oligomer dihydric alcohol as a soft segment, takes quercetin as a chain extender, synthesizes a polyurethane material containing quercetin in a main chain and a metal-ligand coordination cross-linked polyurethane material by a one-pot method, wherein metal ions are used as cross-linking points to connect the polyurethane main chain, and a more flexible network structure is formed.

Inventors

  • WANG MAN
  • YIN YUANYUAN
  • ZHANG RAN
  • ZHAO WEI
  • ZHUANG YUWEI
  • WANG HUAFEN
  • ZHOU SHENGQIANG
  • LIU CHAOHUI
  • YANG JIE
  • HAO XIAOFEI

Assignees

  • 河南省科学院高新技术研究中心

Dates

Publication Date
20260508
Application Date
20260121

Claims (10)

  1. 1. A kind of quercetin Pi Suji polyurethane material, characterized by, the structural formula is as follows: ; Wherein U is a diisocyanate residue, (R) x is a diol oligomer residue, and x is an arbitrary integer of 10 to 100.
  2. 2. The quercetin Pi Suji polyurethane material according to claim 1, wherein the soft segment is a residue of a dihydric alcohol oligomer, the hard segment is a residue formed by reacting quercetin with diisocyanate, the dihydric alcohol oligomer residue is obtained by ring-opening polymerization of one or two monomers of p-dioxanone, lactide, glycolide, epsilon-caprolactone, gamma-butyrolactone, delta-valerolactone, delta-caprolactone, delta-octanolactone, delta-decanolide and delta-dodecalactone, the number average molecular weight is 1-10 kg/mol, the diisocyanate residue is formed by reacting diisocyanate with the dihydric alcohol soft segment, and the diisocyanate is one or two of 4,4' -diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, L-lysine diisocyanate and isophorone diisocyanate.
  3. 3. A novel metal-ligand coordination cross-linked polyurethane material, which is characterized in that a coordination cross-linked structure is formed by a quercetin Pi Sucan base and metal ions in the quercetin Pi Suji polyurethane material in claim 1 or 2, and the structural formula is as follows: ; Wherein M is a metal ion coordinating residue.
  4. 4. A novel metal-ligand coordination cross-linked polyurethane material according to claim 3, wherein the metal ion is one or two of copper chloride, zinc acetate and aluminum chloride.
  5. 5. The method for preparing the quercetin Pi Suji polyurethane material as claimed in claim 1 or 2, which is characterized by comprising the following steps: step S1, drying and dewatering a dihydric alcohol oligomer in a protective atmosphere, and then heating to a temperature above the melting point of the dihydric alcohol oligomer for full melting; s2, adding diisocyanate into the melted diol oligomer in a protective atmosphere, and fully reacting to obtain isocyanate terminated prepolymer; And step S3, adding a quercetin solution into the prepolymer system obtained in the step 2 in a protective atmosphere, fully reacting to obtain a quercetin Pi Suji polyurethane solution, and volatilizing a solvent to obtain a quercetin Pi Suji polyurethane film (Que-PU).
  6. 6. The preparation method of the quercetin Pi Suji polyurethane material is characterized in that the molar ratio of the dihydric alcohol oligomer to the diisocyanate to the quercetin is (0.5-1): 1-8): 0.5-7, the reaction temperature in the steps S2 and S3 is 60-100 ℃, the concentration of the quercetin solution in the step S3 is 0.1-5.0 g/mL, and the solvent of the quercetin solution in the step S3 is N, N-dimethylformamide, toluene, tetrahydrofuran or dimethyl sulfoxide.
  7. 7. The method for preparing a novel metal-ligand coordination cross-linked polyurethane material according to claim 3 or 4, wherein a metal ion solution is added into a quercetin Pi Suji polyurethane solution system under a protective atmosphere, and after full reaction, a solvent is volatilized, so that the novel metal-ligand coordination cross-linked polyurethane film can be obtained.
  8. 8. The method for preparing the novel metal-ligand coordination cross-linked polyurethane material according to claim 7, wherein the reaction temperature is 60-100 ℃, the concentration of the metal ion solution is 0.1-2.0 g/mL, and the solvent of the metal ion solution is N, N-dimethylformamide, toluene, tetrahydrofuran or dimethyl sulfoxide.
  9. 9. Use of the quercetin Pi Suji polyurethane material according to any one of claims 1 or 2 in food metal ion detection probes and food packaging materials.
  10. 10. Use of the novel metal-ligand coordination cross-linked polyurethane material of claim 3 or 4 in biosensors.

Description

Querc Pi Suji polyurethane material, novel metal-ligand coordination crosslinked polyurethane material, and preparation method and application thereof Technical Field The invention relates to the technical field of polyurethane materials, in particular to a quercetin Pi Suji polyurethane material, a novel metal-ligand coordination cross-linked polyurethane material, and a preparation method and application thereof. Background The food is easy to be damaged due to the influence of external physical impact, extrusion, vibration and the like in the process of processing, transporting and storing, and meanwhile, the risk of pollution of microorganisms (bacteria, mold, microzyme), dust, insects and the like is faced, especially fresh food, the deterioration of which in the process of transporting and storing can reduce the safety and the sensory characteristics of the fresh food, and the fresh food is one of the most obvious public health problems threatening the health and life of people. Therefore, food packaging is particularly important, not only is it a "protective barrier" for food from the production end to the consumption end, but also it is a key carrier linking product quality, consumption experience, industrial benefit and environmental sustainability. However, most of the traditional food packaging materials mainly comprise polyethylene and polypropylene, have limited barrier properties, are difficult to meet the lasting fresh-keeping requirement of high-moisture and high-fat foods, have large recycling difficulty and slow degradation speed, can cause problems of soil pollution, marine microplastic and the like, and do not meet the requirement of food packaging on development of safety, fresh-keeping and greenization. Therefore, finding biodegradable and sustainable packaging materials is a current research hotspot. Polyurethane is an emerging high polymer material synthesized by polyisocyanate and hydroxyl-terminated compound, has excellent mechanical properties (such as tensile strength and elongation at break), tear resistance, barrier properties (to oxygen, moisture, carbon dioxide and the like) and good flexibility, can effectively block the influence of external environmental factors on food, prolongs the shelf life of the food, effectively solves the technical bottlenecks of the traditional packaging material in the aspects of safety, sensitivity, freshness preservation durability and the like, and becomes one of key materials for promoting the high-quality development of the food industry. However, with the rapid development of food packaging, a single polyurethane film has failed to meet diversified packaging needs, especially the food is easily oxidized during storage, resulting in degradation of nutrients, flavor change and quality loss, especially lipid-rich foods are more easily deteriorated by oxidation. Therefore, there is a need to develop a polyurethane packaging material which is antibacterial, antioxidant, fresh-keeping, and degradable. On the one hand, researchers introduce polar groups (such as ureido and carbamate groups) into polyurethane to improve the barrier performance to oxygen and moisture, and the hard segment content and the crosslinking degree of the polyurethane are adjusted to realize the accurate regulation and control of the barrier performance of the film, on the other hand, antibacterial agents (such as nano silver, zinc oxide, polyphenol, plant extracts and the like) are also introduced into the polyurethane film in the modes of copolymerization, blending, surface coating or grafting and the like to prepare the antibacterial polyurethane packaging film, so that the antibacterial property and the safety of the film are improved in a long-term quality guarantee mode. More importantly, the biodegradable polyurethane packaging film is prepared by reacting selected bio-based polyols (such as polylactic acid, polycaprolactone, castor oil, starch, etc.) with isocyanate. The film can be degraded into carbon dioxide and water by microorganisms in natural environment, and is environment-friendly. For example, the degradation rate of the castor oil-based polyurethane film can reach 40-60% in soil for 6 months, has good mechanical property and barrier property, and can be used for packaging foods such as fruits, vegetables, bread and the like. And the degradation rate and the service performance of the film are optimized by adjusting the proportion and the structure of the bio-based polyol, so that the packaging requirements of different foods are met. Houbin Li et al also blended curcumin modified castor oil based polyurethane (CWU) with gelatin to prepare an active gelatin based composite film (CWGL) and developed a multi-functional packaging material for efficient storage and monitoring of food. Quercetin (chemical name: 3,3',4',5, 7-pentahydroxy flavone) is a kind of flavone polyphenol compound widely existing in nature, and is widely used in food detection, food packag