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CN-121975287-A - Degradable high-hydrophilicity PCL composite film and preparation method thereof

CN121975287ACN 121975287 ACN121975287 ACN 121975287ACN-121975287-A

Abstract

The invention discloses a degradable high-hydrophilicity PCL composite film and a preparation method thereof. The degradable high-hydrophilicity PCL composite film comprises, by mass, 80-85 parts of PCL, 10-13 parts of a hydrophilic auxiliary agent, 1-2 parts of a compatibility regulator, 2-3 parts of an auxiliary plasticizer, 120-140 parts of a solvent and 0.3-0.5 part of an antioxidant, wherein the hydrophilic auxiliary agent is prepared by compounding sodium carboxymethyl cellulose, low-molecular-weight trehalose phosphate and a polyglycerol-polylactic acid segmented copolymer (PG-PLA) according to a mass ratio of (1.5-2.5) to 1:1. The degradable high-hydrophilicity PCL composite film and the preparation method thereof remarkably improve the hydrophilicity of the PCL film, have moderate flexibility and stable performance, improve the safety, and have the advantages of simple preparation method, easy operation, high efficiency and easy production and popularization.

Inventors

  • ZHANG DASHUAI
  • REN LIYING
  • SHI ZAIFENG

Assignees

  • 海南师范大学

Dates

Publication Date
20260505
Application Date
20260303

Claims (10)

  1. 1. The degradable high-hydrophilicity PCL composite film is characterized by comprising, by mass, 80-85 parts of PCL, 10-13 parts of a hydrophilic auxiliary agent, 1-2 parts of a compatibility regulator, 2-3 parts of an auxiliary plasticizer, 120-140 parts of a solvent and 0.3-0.5 part of an antioxidant; The hydrophilic auxiliary agent is prepared by compounding sodium carboxymethyl cellulose, low-molecular-weight trehalose phosphate and polyglycerol-polylactic acid segmented copolymer according to a mass ratio of (1.5-2.5) to 1:1.
  2. 2. The degradable high-hydrophilicity PCL composite membrane according to claim 1, wherein the preparation method of the low-molecular-weight trehalose phosphate is characterized in that trehalose and a phosphorylating reagent are mixed according to a molar ratio of 1:1.2-1.5, reacted for 2-3 hours under the condition that the temperature of 60-70℃, pH is 7.0-7.5, and the low-molecular-weight trehalose phosphate is obtained through centrifugation, washing, dialysis and freeze drying.
  3. 3. The degradable high-hydrophilicity PCL composite film according to claim 2, wherein the phosphorylating agent is a mixture of sodium tripolyphosphate and sodium trimetaphosphate in a mass ratio of (5-7): 1.
  4. 4. The degradable highly hydrophilic PCL composite film according to any one of claims 1 to 3, characterized in that the molecular weight of the polyglycerin-polylactic acid block copolymer is 5000 to 8000, and the mass ratio of the polyglycerin segment to the polylactic acid segment is 1:1.5 to 2.0.
  5. 5. The degradable high-hydrophilicity PCL composite film according to any one of claims 1 to 3, wherein the preparation method of the polyglycerol-polylactic acid segmented copolymer is characterized in that polyglycerol and polylactic acid with the mass ratio of 1 (2 to 2.5) are reacted for 3 to 5 hours under the catalysis of stannous octoate at 120 to 130 ℃ to obtain the polyglycerol-polylactic acid segmented copolymer.
  6. 6. A degradable highly hydrophilic PCL composite film according to any one of claims 1-3, characterized in that the PCL has a number average molecular weight of 50000-80000.
  7. 7. The degradable high-hydrophilicity PCL composite film according to any one of claims 1 to 3, wherein the compatibility regulator is gamma-aminopropyl triethoxysilane, the auxiliary plasticizer is PEG600, the antioxidant is bis (3, 5-di-tert-butyl-4-hydroxybenzyl phosphonic acid monoethyl ester) calcium, and the solvent is chloroform and dimethyl sulfoxide which are compounded according to a volume ratio of 8:2.
  8. 8. A method for preparing a degradable highly hydrophilic PCL composite membrane according to any one of claims 1 to 7, characterized in that a solvent evaporation membrane method is adopted, comprising the following steps: (1) Drying PCL to remove water, dissolving in a solvent, adding a hydrophilic auxiliary agent, a compatibility regulator, an antioxidant and an auxiliary plasticizer, uniformly stirring, performing ultrasonic dispersion on the liquid, and performing vacuum defoaming to obtain a mixed liquid; (2) Casting the mixture obtained in the step (1) on a die, and controlling the film thickness to be 0.1-0.2mm; (3) And (3) adopting three-stage temperature control drying, thoroughly removing the solvent, cooling, cutting and sterilizing to obtain a finished product.
  9. 9. The preparation method of the ultrasonic foam powder of claim 8, wherein in the step (1), the ultrasonic power is 300W, the ultrasonic time is 15-20min, the vacuum degree of vacuum defoaming is 0.08-0.1MPa, and the defoaming time is 15-20min; In the step (2), the casting ambient temperature is 25-30 ℃, the humidity is 40-50%, and the casting speed is 0.3-0.5m/min.
  10. 10. The preparation method according to claim 8 or 9, wherein in the step (3), the specific parameters of the three-stage temperature-controlled drying are 30-35 ℃ for 2-3h,40-45 ℃ for 4-5h and 50 ℃ for 12h.

Description

Degradable high-hydrophilicity PCL composite film and preparation method thereof Technical Field The invention relates to a degradable high-hydrophilicity PCL composite film and a preparation method thereof, belonging to the technical field of degradable high polymer materials. Background Polycaprolactone (PCL for short) is an organic high molecular polymer with good biocompatibility, biodegradability and drug permeability, the chemical formula is (C 6H10O2) n, and the chemical synthesis high molecular material is prepared by ring-opening polymerization of epsilon-caprolactone under the condition of taking dihydroxyl or trihydroxy as an initiator and taking a metal organic compound (such as tetraphenyl tin) as a catalyst. Polycaprolactone has good processability, good organic polymer compatibility, and can be used as a cell growth support material. Polycaprolactone also has good drug permeability, especially small molecule drugs, and because polycaprolactone also has good biodegradability, polycaprolactone is mainly used in the aspect of controlled release carriers, and because polycaprolactone has a special molecular structure, namely a longer methylene link, polycaprolactone needs two to four years to be completely absorbed and removed by the body, so polycaprolactone is more suitable for preparing long-acting slow release drugs, and has been approved by the FDA (food and drug administration). However, due to the hydrophobic nature of polycaprolactone, the following problems are that 1) the hydrophilic nature of the polycaprolactone is extremely poor, the water-soluble medicine is difficult to uniformly load into the membrane and easy to agglomerate, the polycaprolactone can only be used for loading the fat-soluble medicine, the medicine application range is greatly limited, 2) body fluid is difficult to permeate into the membrane, the medicine cannot be dissolved out or released by diffusion, the overall release speed is obviously slow, initial burst release is insufficient in the early stage, effective treatment concentration is difficult to be achieved quickly, the hydrophobic barrier exists all the time in the later stage, release stagnation (release interruption) is easy to occur, stable administration cannot be achieved, 3) the hydrophobic membrane is not compatible with the water-based body fluid and tissue interface, protein adsorption and foreign body reaction are easy to be initiated, even the medicine is wrapped by fibrous tissues, the medicine is difficult to diffuse from the membrane surface to focus or target tissues, and the actual curative effect is reduced. Furthermore, the pure PCL film has insufficient flexibility, and intestinal mucosa can be scratched during administration. In the prior art, a report on a PCL film is also provided, for example, a patent application with the application number of CN202310001923.8 discloses a PLA and modified PCL blended degradable heat-shrinkable film, wherein the plasticizer adopts epoxidized soybean oil, the preparation method is melt plasticizing-extrusion granulating-blow molding, the preparation method is mainly used in the packaging field, the core aims at improving the heat-shrinkable performance, the preparation method is not suitable for oral drug delivery, the process is complex, the modified PCL is required to be additionally prepared, and the large-scale application is not facilitated. Patent application No. CN201610200344.6 discloses a PCL slow-release membrane loaded with a drug, but the technical problems of poor hydrophilicity and the like of the PCL membrane are not solved. Disclosure of Invention The invention provides a degradable high-hydrophilicity PCL composite film and a preparation method thereof, which solve the technical problem of insufficient hydrophilicity of the traditional PCL film, further improve the flexibility of the PCL film, improve the safety, improve the preparation efficiency, and can be used as a slow-release drug delivery carrier and the like. In order to solve the technical problems, the technical scheme adopted by the invention is as follows: The degradable high-hydrophilicity PCL composite film comprises, by mass, 80-85 parts of PCL, 10-13 parts of a hydrophilic auxiliary agent, 1-2 parts of a compatibility regulator, 2-3 parts of an auxiliary plasticizer, 120-140 parts of a solvent and 0.3-0.5 part of an antioxidant; the hydrophilic auxiliary agent is prepared by compounding sodium carboxymethyl cellulose, low molecular weight trehalose phosphate (MW < 1000) and polyglycerol-polylactic acid segmented copolymer (PG-PLA) according to a mass ratio of (1.5-2.5) to 1:1. The hydrophilic auxiliary agent adopted by the application is compounded by sodium carboxymethyl cellulose, low molecular weight trehalose phosphate and polyglycerol-polylactic acid segmented copolymer, so that the hydrophilic property of the PCL composite film is effectively improved, and meanwhile, the compatibility with PCL can be effectively