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CN-121779652-B - Preparation method of degradable polyurethane material

CN121779652BCN 121779652 BCN121779652 BCN 121779652BCN-121779652-B

Abstract

The invention discloses a preparation method of a degradable polyurethane material, which comprises the following steps of (1) mixing a decalactone monomer, an alcohol initiator and a ring-opening polymerization catalyst in inert atmosphere, dissolving a reaction product in an organic solvent after reaction, settling the reaction product in cold methanol, filtering and drying to obtain a polydecactone prepolymer, wherein the molar ratio of the alcohol initiator to the decalactone monomer is 1:100-600, (2) vacuumizing the polydecactone prepolymer at 20-100 ℃ for 4-20 h, then adding isocyanate and a polycondensation reaction catalyst into the polydecane prepolymer, reacting for 1-20 h at 20-120 ℃ to obtain a polyurethane prepolymer, and (3) mixing the polyurethane prepolymer obtained by reaction, cyclodextrin and the organic solvent with the catalyst, reacting for 12-24 h at 60-120 ℃ and drying the obtained product to obtain the polyurethane material. The polyurethane material has good degradability and mechanical property.

Inventors

  • ZHOU YUMING
  • Tong Chuangyi
  • LIANG SHUANG
  • HE MAN
  • HUANG JINGYI
  • Lu Tianle
  • REN YINGLI

Assignees

  • 东南大学

Dates

Publication Date
20260505
Application Date
20260305

Claims (6)

  1. 1. The preparation method of the degradable polyurethane material is characterized by comprising the following steps of: (1) Mixing a decalactone monomer, an alcohol initiator and a ring-opening polymerization catalyst in inert atmosphere, dissolving a reaction product in an organic solvent after reaction, settling the reaction product in cold methanol, filtering and drying to obtain a polydecanolide prepolymer, wherein the molar ratio of the alcohol initiator to the decalactone monomer is 1:100-600, the decalactone monomer is delta decalactone or delta decalactone, the ring-opening polymerization catalyst is 1,5, 7-triazabicyclo [4.4.0] dec-5-ene or stannous octoate, and the alcohol initiator is benzyl alcohol or terephthalyl alcohol; (2) Vacuumizing a polydecanolide prepolymer for 4-20 hours at 20-100 ℃, and then adding isocyanate and a polycondensation catalyst into the polydecanolide prepolymer, wherein the polycondensation catalyst is at least one of stannous octoate, dibutyltin dilaurate or 1, 4-diazabicyclo [2.2.2] octane, and the addition amount of the polycondensation catalyst is 6.25% -8% of the mass of the polydecanolide prepolymer, and reacting for 1-20 hours at 20-120 ℃ to obtain a polyurethane prepolymer; (3) Mixing polyurethane prepolymer obtained by reaction, cyclodextrin and an organic solvent with a catalyst, reacting for 12-24 hours at 60-120 ℃, and drying the obtained product to obtain the degradable polyurethane material, wherein the catalyst is N.N-dibutyl formamide, and the addition amount of the catalyst is 2-3% of the mass of the polyurethane prepolymer.
  2. 2. The method according to claim 1, wherein in the step (1), the number average molecular weight of the polydecanolactone prepolymer is 3,000 to 40,800Da.
  3. 3. The method according to claim 1, wherein in the step (1), the amount of the catalyst for ring-opening polymerization is 0.1% to 1% by mass of the decalactone monomer.
  4. 4. The preparation method of the polyurethane foam as claimed in claim 1, wherein in the step (2), the isocyanate is one of hexamethylene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate, and the molar ratio of the polydecanolactone prepolymer to the isocyanate is 1:1-10.
  5. 5. The preparation method of the polyurethane foam according to claim 1, wherein in the step (3), the cyclodextrin is alpha-cyclodextrin or beta-cyclodextrin, the mass ratio of the polyurethane prepolymer to the cyclodextrin is 10-15:1, and the organic solvent is one of dichloromethane, toluene, tetrahydrofuran or N, N-dimethylformamide.
  6. 6. The method of claim 1, wherein in the step (3), the drying temperature is 60-80 ℃ and the drying time is not less than 12 hours.

Description

Preparation method of degradable polyurethane material Technical Field The invention relates to a preparation method of a degradable polyurethane material. Background Polyurethane (PU) is a polymer material with excellent performance and wide application, which is produced by reacting isocyanate (hard segment) and polyol (soft segment). By adjusting the chemical structure and proportions of the soft and hard segments, a variety of products can be made, ranging from soft sponges to hard plastics, from highly elastic elastomers to tough coatings. However, the commercial polyurethane products at present mainly depend on non-renewable petroleum-based raw materials, have poor degradation capability in natural environment and difficult recycling, are often treated by incineration or landfill after being used, and easily cause the problem of unavoidable environmental pollution. The main reasons for the difficulty in degrading petroleum-based polyurethane can be summarized as that firstly, the main chain of the petroleum-based polyurethane contains a large number of structurally stable urethane bonds and benzene ring structures, the petroleum-based polyurethane shows higher chemical inertness to the attack of microorganisms and enzymes, and secondly, the soft segment formed by petroleum-based polyether is endowed with excellent flexibility, but usually lacks sensitive functional groups which are easy to hydrolyze or photodegradation, and in addition, the dense crosslinked network structure further prevents permeation and diffusion of degradation media such as water, enzymes and the like. In order to improve the degradability of polyurethane materials, the prior art has developed new polyols using renewable biomass raw materials, or introduced sensitive bond segments in the molecular chain that are prone to hydrolysis or photolysis. However, the prior art can reduce the mechanical properties (such as strength and toughness) of polyurethane while improving the degradability, and has the problem that the degradability and the mechanical properties are difficult to be compatible. Disclosure of Invention The invention aims to provide a method for preparing a polyurethane material with good degradability and mechanical properties. The preparation method of the degradable polyurethane material comprises the following steps: (1) Mixing a decalactone monomer, an alcohol initiator and a ring-opening polymerization catalyst in inert atmosphere, dissolving a reaction product in an organic solvent after the reaction, settling the reaction product in cold methanol, filtering and drying to obtain a polydecactone prepolymer, wherein the molar ratio of the alcohol initiator to the decalactone monomer is 1:100-600, and the dosage of the ring-opening polymerization catalyst is 0.1% -1% of the mass of the decalactone monomer; (2) Vacuumizing the polydecanolide prepolymer for 4-20 hours at 20-100 ℃, adding isocyanate and a polycondensation catalyst into the polydecanolide prepolymer, and reacting for 1-20 hours at 20-120 ℃ to obtain a polyurethane prepolymer; (3) Mixing the polyurethane prepolymer obtained by the reaction, cyclodextrin and an organic solvent with a catalyst, reacting for 12-24 hours at 60-120 ℃, and drying the obtained product in a vacuum oven at 60 ℃ overnight to obtain the degradable polyurethane material. In the step (1), the decalactone monomer is delta decalactone or delta decalactone. The ring-opening polymerization catalyst is one of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, stannous octoate or N.N-dibutyl formamide (CAS number 761-65-9), and the alcohol initiator is one of methanol, ethanol, benzyl alcohol, ethylene glycol, terephthalyl alcohol, glycerol or pentaerythritol. The molar ratio of the alcohol initiator to the decalactone monomer is controlled to be 1:100-600, so that the molecular weight distribution (3,000-40,800 Da) of the decalactone prepolymer can be effectively regulated and controlled, the number average molecular weight (M n) of the decalactone prepolymer is in a range suitable for subsequent polyurethane synthesis, and the final polyurethane material is ensured to have excellent mechanical strength and flexibility. The catalyst dosage is controlled to be 0.1% -1% of the monomer mass, so that the reaction can maintain a higher reaction rate at normal temperature, the negative influence of residual catalyst on the biocompatibility of the material is avoided, the catalyst is dissolved by adopting an organic solvent and then is settled in cold methanol, unreacted monomers and catalyst impurities can be effectively removed, the purity of the prepolymer is improved, and a foundation is laid for the subsequent synthesis of polyurethane with regular structure. In the step (2), the isocyanate is one of hexamethylene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate, and the molar ratio of the polydecanolactone prepolymer to the isocyanate (calculated by functional groups, the molar