CN116271249A - Fluorine oil filled poly (4-hydroxybutyrate) composite fiber membrane patch, preparation method thereof and anti-adhesion membrane - Google Patents
Fluorine oil filled poly (4-hydroxybutyrate) composite fiber membrane patch, preparation method thereof and anti-adhesion membrane Download PDFInfo
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- CN116271249A CN116271249A CN202310315780.8A CN202310315780A CN116271249A CN 116271249 A CN116271249 A CN 116271249A CN 202310315780 A CN202310315780 A CN 202310315780A CN 116271249 A CN116271249 A CN 116271249A
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- hydroxybutyrate
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- block copolymer
- composite fiber
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- 238000003756 stirring Methods 0.000 claims description 8
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- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 claims description 6
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Images
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
Abstract
The invention belongs to the technical field of medical instruments, and discloses a fluorine oil filled poly (4-hydroxybutyrate) composite fiber membrane patch, a preparation method thereof and an anti-adhesion membrane. The composite fiber membrane patch comprises 45-94.9 wt% of poly (4-hydroxybutyrate), 0.001-50 wt% of organic fluoro-poly (4-hydroxybutyrate) block copolymer and 5-20 wt% of fluorine oil, wherein the organic fluoro-poly (4-hydroxybutyrate) block copolymer effectively improves the affinity between a poly (4-hydroxybutyrate) substrate and the fluorine oil so as to improve the retention time of the fluorine oil, and meanwhile, the characteristics that the fluorine oil can be lost and the poly (4-hydroxybutyrate) can be degraded are utilized, so that the composite fiber membrane has excellent anti-adhesion property and can promote tissue cells to grow in quickly so as to repair the abdominal wall defect with high efficiency.
Description
Technical Field
The invention belongs to the technical field of medical instruments, and particularly relates to a fluorine oil filled poly (4-hydroxybutyrate) composite fiber membrane patch, a preparation method thereof and an anti-adhesion membrane.
Background
Peritoneal defects caused by congenital disease factors, surgical wounds, tumor resection operations and the like cause medical expenditure of hundreds of billions of yuan each year, and simultaneously bring great pain to patients, and tension-free repair is an important way for solving the problems. Patches are commonly used clinically to achieve tensionless repair of peritoneal defects, polypropylene and polyester patches are common medical devices for treating peritoneal defects. However, polypropylene and polyester patches are prone to severe visceral adhesion and inflammatory reactions in actual use, and conventional polyester patches also have problems of poor interaction with tissue cells, acidic degradation products, susceptibility to inflammatory reactions (such as polylactic acid, polycaprolactone, and polylactic acid-glycolic acid copolymers), and the like.
In recent years, poly (4-hydroxybutyrate) (P4 HB) has the characteristics of flexibility, controllable degradability, good biocompatibility and the like, is concerned by scientific research and enterprises, and P4HB is the only polyhydroxyalkanoate approved by FAD for clinical application at present.
The half-life of the degradation product 4-hydroxybutyrate of P4HB is only 27min, eventually with CO 2 The form of (2) is rapidly metabolized and discharged from the body, can not be accumulated in the body, and can avoid causing inflammatory reaction. In addition, 4 hydroxybutyrate (4 HB) promotes the expression of macrophage endogenous antibacterial peptide (AMP, cathelicidin LL-37), thereby greatly reducing the incidence of clinical surgical infection and inflammation. Currently, commercial P4HB patches have been used in the treatment of hernias and breast lifting surgery (US 10136982 B2). However, the P4HB patch still has adhesion during actual use, severely affecting the recovery process of the patient.
Disclosure of Invention
In order to develop a novel fluorine oil filled poly (4-hydroxybutyrate) fiber membrane to solve the adhesion problem in the peritoneal defect treatment process, the invention provides a fluorine oil filled poly (4-hydroxybutyrate) fiber membrane, a preparation method thereof and an anti-adhesion membrane.
In a first aspect, the present application provides a composite fiber membrane patch employing the following technical scheme:
a composite fibrous membrane patch comprising 45 to 94.9wt% of poly (4-hydroxybutyrate), 0.001 to 50wt% of an organic fluoro-poly (4-hydroxybutyrate) block copolymer, and 5 to 20wt% of a fluorooil.
In some specific embodiments, the poly (4-hydroxybutyrate) has a weight average molecular weight of 100000 ～ 300000.
In some specific embodiments, the organic fluoro-poly (4-hydroxybutyrate) block copolymer is selected from one or more of a nonafluoropentyl-poly (4-hydroxybutyrate) block copolymer, a tridecyl-poly (4-hydroxybutyrate) block copolymer, a heptadecyl-fluoro-nonyl-poly (4-hydroxybutyrate) block copolymer, a hexafluorobutyl-poly (4-hydroxybutyrate) block copolymer, a dodecafluoro heptyl-poly (4-hydroxybutyrate) block copolymer, and an octafluoropentyl-poly (4-hydroxybutyrate) block copolymer.
In some specific embodiments, the organofluoro-poly (4-hydroxybutyrate) block copolymer is prepared from: mixing organic fluoric acid and poly (4-hydroxybutyrate) with hydroxyl group at single end according to the molar input ratio of (1.0-1.5), adding tetrabutyl titanate as catalyst, heating to 150-170 ℃ under stirring, reacting for 10-14 h, and purifying to obtain the organic fluoric-poly (4-hydroxybutyrate) block copolymer.
In some specific embodiments, the fluorooil is selected from one or more of perfluoro (2-n-butyltetrahydrofuran), perfluoro tributylamine, perfluoro decalin, perfluoro methyl decalin, perfluoro tripropylamine, and perfluoro polyether.
In a second aspect, the present application further provides a method for preparing the composite fiber membrane patch, which adopts the following technical scheme: and uniformly mixing the poly (4-hydroxybutyrate) and the organic fluorine-poly (4-hydroxybutyrate) block copolymer, spinning to obtain a prefabricated film, and pouring fluorine oil into the prefabricated film to obtain the composite fiber film patch.
In some embodiments, the spinning is performed by a method selected from one or more of melt spinning, solution spinning, and electrospinning.
In some specific embodiments, the method of priming is: the fluorine oil is supported on the inside and the surface of the prefabricated film by a soaking and/or coating mode.
In a third aspect, the present application further provides an anti-adhesion film, which adopts the following technical scheme:
an anti-adhesion film at least comprises the composite fiber film patch and/or the composite fiber film patch prepared by the method.
In some specific embodiments, the anti-adhesion membrane further comprises one or more of an anti-cancer drug, an anti-inflammatory drug, and an anti-adhesion drug.
The beneficial effects are that:
the composite fiber membrane patch provided by the invention comprises poly (4-hydroxybutyrate), an organic fluorine-poly (4-hydroxybutyrate) block copolymer and fluorine oil, wherein the organic fluorine-poly (4-hydroxybutyrate) block copolymer is added into the poly (4-hydroxybutyrate) for modification, so that the affinity between a prefabricated membrane and the fluorine oil is improved while the mechanical property is improved, the fluorine oil can be better loaded on the prefabricated membrane, the retention time of the fluorine oil on the composite fiber membrane patch is prolonged, and the characteristics that the fluorine oil can be lost and the poly (4-hydroxybutyrate) can be degraded are utilized, so that the prepared composite fiber membrane patch has good anti-blocking property, can be used as an anti-blocking membrane, and has excellent performance.
Drawings
FIG. 1 is a view showing the composite fiber membrane patch according to example 1 of the present invention after 7d of repair of a peritoneal defect;
FIG. 2 is a diagram showing the composite fiber membrane patch according to example 1 of the present invention after 24d of repair of a peritoneal defect;
fig. 3 is a graph of the composite fiber membrane patch provided in comparative example 1 after 24d of repair of a peritoneal defect.
Detailed Description
Based on the deep knowledge and understanding of patch materials used in the treatment of peritoneal defects, the inventor selects a prefabricated film obtained by taking poly (4-hydroxybutyrate) as a matrix material and adding an organic fluorine-poly (4-hydroxybutyrate) block copolymer into the matrix material for modification, and finally infuses fluorine oil into the prefabricated film to obtain a composite fiber film patch, and the three components cooperate to ensure that the composite fiber film patch has good mechanical property, excellent biodegradability and lower surface energy, can promote tissue cells to grow into rapidly in the later stage of peritoneal defect repair to realize the efficient repair of abdominal wall defect, and has good anti-adhesion effect.
In the present invention, the composite fiber membrane patch comprises 45 to 94.9wt% of poly (4-hydroxybutyrate), 0.001 to 50wt% of organic fluoro-poly (4-hydroxybutyrate) block copolymer and 5 to 10wt% of fluorine oil.
In some specific embodiments, the poly (4-hydroxybutyrate) has a weight average molecular weight of 100000 ～ 300000, which may specifically be 100000, 110000, 130000, 160000, 180000, 200000, 240000, 280000, 300000, or any value therebetween.
In some specific embodiments, the mass fraction of poly (4-hydroxybutyrate) in the composite fiber film patch may be 45wt%, 50wt%, 55wt%, 60wt%, 63wt%, 68wt%, 70wt%, 75wt%, 77wt%, 80wt%, 85wt%, 90wt%, 93wt%, 94.9wt%, or any value therebetween.
In the present invention, the organofluoro-poly (4-hydroxybutyrate) block copolymer refers to a product obtained by reacting poly (4-hydroxybutyrate) with a single-ended hydroxyl group-containing poly (4-hydroxybutyrate) with a polyfluoro organic acid.
In some embodiments, the polyfluoro organic acid may be, in particular but not limited to, one or more of nonafluorovaleric acid, tridecafluorooctanoic acid, heptadecafluorononanoic acid, hexafluorobutyric acid, dodecafluoroheptanoic acid, and octafluorovaleric acid.
In some embodiments, the poly (4-hydroxybutyrate) in the organofluoro-poly (4-hydroxybutyrate) block copolymer has a weight average molecular weight of 10000 to 100000, which may specifically be 10000, 20000, 30000, 50000, 70000, 80000, 100000, or any value therebetween.
The poly (4-hydroxybutyrate) in the organofluoro-poly (4-hydroxybutyrate) block copolymer has a smaller weight average molecular weight than the poly (4-hydroxybutyrate) used in the composite fiber membrane patch, enabling the realization of the desired modification effect.
In some embodiments, the preparation of the organofluoro-poly (4-hydroxybutyrate) block copolymer is specifically: taking organic fluoric acid and poly (4-hydroxybutyrate) with hydroxyl at a single end according to the molar input ratio of (1.0-1.5), adding tetrabutyl titanate as a catalyst, heating to 150-170 ℃ under stirring, reacting for 10-14 h, and purifying to obtain the organic fluoric-poly (4-hydroxybutyrate) block copolymer.
In the present invention, the organofluoro-poly (4-hydroxybutyrate) block copolymer may be, but is not limited to, one or more of a nonafluoropentyl-poly (4-hydroxybutyrate) block copolymer, a trideceth-luorooctyl-poly (4-hydroxybutyrate) block copolymer, a heptadecafluorononyl-poly (4-hydroxybutyrate) block copolymer, a hexafluorobutyl-poly (4-hydroxybutyrate) block copolymer, a dodecafluoroheptyl-poly (4-hydroxybutyrate) block copolymer, and an octafluoropentyl-poly (4-hydroxybutyrate) block copolymer.
In some specific embodiments, the mass fraction of the organofluoro-poly (4-hydroxybutyrate) block in the composite fibrous membrane patch may be, but is not limited to, 0.001wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, or any value therebetween.
In the present invention, the fluorine oil may be specifically but not limited to one or more of perfluoro (2-n-butyltetrahydrofuran), perfluoro tributylamine, perfluoro decalin, perfluoro methyl decalin, perfluoro tripropylamine and perfluoro polyether. By adding the fluorine oil into the composite fiber membrane patch, the fluorine oil gradually runs off along with the time, and plays a role in cooperation with poly (4-hydroxybutyrate) and fluoroalkyl block modification (4-hydroxybutyrate), so that tissue cells are promoted to grow in rapidly, and the high-efficiency repair of the abdominal wall defect is realized.
In some specific embodiments, the mass fraction of the fluorooil in the composite fiber film patch may be 5wt%, 8wt%, 10wt%, 15wt%, 20wt%, or any value therebetween.
In the invention, the preparation method comprises the steps of uniformly mixing poly (4-hydroxybutyrate) and organic fluorine-poly (4-hydroxybutyrate) block copolymer, spinning to obtain a prefabricated film, and then pouring fluorine oil into the prefabricated film to obtain the composite fiber film patch.
In some embodiments, the method of spinning the mixture of poly (4-hydroxybutyrate) and organofluoro-poly (4-hydroxybutyrate) block copolymer may specifically be, but is not limited to, one or more of melt spinning, solution spinning, and electrostatic solution spinning.
Melt spinning refers to: drying the mixture of poly (4-hydroxybutyrate) and organic fluorine-poly (4-hydroxybutyrate) block copolymer at 35-45 ℃ for 20-25 h, and spinning at 150-180 ℃ and twin screw speed of 15-30 r/min to obtain the prefabricated film.
Solution spinning refers to: adding poly (4-hydroxybutyrate) and organic fluorine-poly (4-hydroxybutyrate) block copolymer into N-methyl pyrrolidone, stirring for 20-25 h to obtain spinning solution, and spinning under the conditions that the temperature of the spinning solution is 30-40 ℃ and the coagulation bath temperature is 5-10 ℃ to obtain a prefabricated film; wherein the concentration of the spinning solution used in the wet spinning is 15-30wt%.
Electrostatic solution spinning refers to: adding poly (4-hydroxybutyrate) and organic fluorine-poly (4-hydroxybutyrate) block copolymer into trifluoroethanol, uniformly mixing to obtain spinning solution, and spinning under the conditions of 15-25 kV voltage, 1-2 mL/h injection speed and 15-20 cm distance between a needle and a receiver to obtain a prefabricated film; wherein the concentration of the spinning solution used in the electrostatic solution spinning is 10-20wt%. In some embodiments, the method of infusing the fluorine oil into the preformed film may be, but is not limited to, dipping and/or coating.
Wherein, soaking means: placing the prefabricated film in fluorine oil to enable the fluorine oil to completely permeate the prefabricated film, and after standing for a period of time, pouring a certain amount of fluorine oil on the prefabricated film to enable the fluorine oil content in the finally prepared composite fiber film patch to be 5-20wt%.
Coating refers to: and (3) coating a certain amount of fluorine oil on both sides of the prefabricated film by brushing, wiping, knife coating or spraying, and standing for a period of time to enable the fluorine oil to permeate into the prefabricated film to obtain the composite fiber film patch.
The application also provides an anti-adhesion membrane which at least comprises the composite fiber membrane patch, wherein the mechanical strength of the anti-adhesion membrane is greater than 32.1MPa, the strength requirement of the abdominal wall defect repair patch is met, the anti-adhesion membrane has low specific surface energy and good anti-adhesion performance, and tissue cell adhesion and proliferation can be induced after implantation so as to realize efficient peritoneal repair.
In some embodiments, the anti-adhesion film further comprises one or more of an anti-cancer drug, an anti-inflammatory drug, and an anti-adhesion drug, thereby imparting a specific biological function to the anti-adhesion film.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be taken as limiting the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Preparation example 1.
The preparation example is used for illustrating the preparation of heptadecafluorononyl-poly (4-hydroxybutyrate) block copolymer, and specifically comprises the following steps:
s1, taking 1.2mol of heptadecafluorononanoic acid and 1.0mol of poly (4-hydroxybutyrate) with hydroxyl group at a single end (the number average molecular weight is 3 ten thousand, the molecular weight distribution is 1.2, the same applies below), adding 0.5wt% of tetrabutyl titanate as a catalyst, and uniformly mixing to obtain a reaction solution;
s2, heating the reaction liquid to 160 ℃ under the condition of stirring, and reacting for 12 hours to obtain a crude product;
s3, dissolving the product by using chloroform, stirring for 12 hours, and filtering to remove undissolved substances to obtain the heptadecafluorononyl-poly (4-hydroxybutyrate) block copolymer.
Wherein the input amount of tetrabutyl titanate is 0.5 percent of the input total mass of heptadecafluorononanoic acid and poly (4-hydroxybutyrate) containing hydroxyl at single end.
Preparation example 2.
This preparation example is intended to illustrate the preparation of tridecafluorooctyl-poly (4-hydroxybutyrate) block copolymer, comprising the following steps:
s1, taking 1.5mol of tridecafluorooctanoic acid and 1.0mol of poly (4-hydroxybutyrate) with hydroxyl contained in a single end, adding tetrabutyl titanate as a catalyst, and uniformly mixing to obtain a reaction solution;
s2, heating the reaction liquid to 170 ℃ under the condition of stirring, and reacting for 14 hours to obtain a crude product;
s3, dissolving the product by using chloroform, stirring for 12 hours, and filtering to remove undissolved substances to obtain the tridecafluorooctyl-poly (4-hydroxybutyrate) block copolymer.
Wherein the input amount of tetrabutyl titanate is 0.5 percent of the input total mass of tridecafluorooctanoic acid and poly (4-hydroxybutyrate) containing hydroxyl at a single end.
Example 1.
In this example, a composite fiber membrane patch is provided, comprising 80wt% poly (4-hydroxybutyrate), 10wt% heptadecafluorononyl-poly (4-hydroxybutyrate) block copolymer provided in preparation example 1, and 10wt% perfluorodecalin, the preparation of the composite fiber membrane patch specifically comprising the steps of:
s1, uniformly mixing 80 parts of poly (4-hydroxybutyrate) and 10 parts of heptadecafluorononyl-poly (4-hydroxybutyrate) block copolymer in trifluoroethanol to obtain a spinning solution with the concentration of 15 wt%;
s2, carrying out electrostatic spinning on the spinning solution under the conditions of 20kV voltage, 1mL/h injection speed, 15G flat head needle with needle specification and 15cm distance between the needle and a receiver to obtain a prefabricated film;
and S3, completely immersing the prefabricated film in perfluorodecalin, and immersing the prefabricated film until 10 parts of perfluorodecalin is poured on the prefabricated film to obtain the composite fiber film patch.
Fig. 1 and 2 are experimental diagrams after 7d and 24d peritoneal defect repair using the composite fiber membrane patch provided in this example. As can be seen from the figure, the composite fiber membrane patch still maintains a good form, is not adhered to viscera, and has a good recovery state at the peritoneal defect, which indicates that the composite fiber membrane patch provided by the embodiment has good anti-adhesion property and capability of promoting adhesion and proliferation of tissue cells.
Example 2.
In this example, a composite fiber membrane patch is provided, comprising 70wt% poly (4-hydroxybutyrate), 15wt% tridecafluorooctyl-poly (4-hydroxybutyrate) block copolymer provided in preparation example 2, and 15wt% perfluorodecalin, the preparation of the composite fiber membrane patch specifically comprising the steps of:
s1, uniformly mixing 70 parts of poly (4-hydroxybutyrate) and 15 parts of tridecyl-poly (4-hydroxybutyrate) block copolymer in an internal mixer, drying at 40 ℃ for 24 hours, and carrying out melt spinning on the mixture of the poly (4-hydroxybutyrate) and the tridecyl-poly (4-hydroxybutyrate) block copolymer under the conditions that the temperature is 150-180 ℃ and the twin screw speed is 15-30 r/min to obtain a prefabricated film;
s2, completely immersing the prefabricated film in perfluorodecalin, and soaking until 15 parts of perfluorodecalin is poured on the prefabricated film to obtain the composite fiber film patch.
Example 3.
In this example, there is provided a composite fiber membrane patch comprising 80wt% of poly (4-hydroxybutyrate), 5wt% of tridecafluorooctyl-poly (4-hydroxybutyrate) block copolymer provided in preparation example 2, 5wt% of heptadecafluorononyl-poly (4-hydroxybutyrate) block copolymer provided in preparation example 1, and 10wt% of perfluoro-n-butyl tetrahydrofuran, the preparation of the composite fiber membrane patch specifically comprising the steps of:
s1, uniformly mixing 80 parts of poly (4-hydroxybutyrate), 5 parts of tridecafluorooctyl-poly (4-hydroxybutyrate) block copolymer and 5 parts of heptadecafluorononyl-poly (4-hydroxybutyrate) block copolymer in N-methylpyrrolidone to obtain a spinning solution with the concentration of 20 wt%;
s2, carrying out wet spinning on the spinning solution at the temperature of 35 ℃ and the coagulation bath temperature of 10 ℃ to obtain a prefabricated film;
and S3, completely immersing the prefabricated film in perfluoro-n-butyl tetrahydrofuran, and immersing the prefabricated film into 10 parts of perfluoro-n-butyl tetrahydrofuran to obtain the composite fiber film patch.
Comparative example 1.
In the comparative example, poly (4-hydroxybutyrate) is used as a raw material, and a composite fiber membrane patch is prepared by adopting an electrostatic spinning method, and the specific steps are as follows:
s1, dissolving poly (4-hydroxybutyrate) in trifluoroethanol, and uniformly mixing to obtain a spinning solution with the concentration of 15 wt%;
s2, carrying out electrostatic spinning on the spinning solution under the conditions of 20kV voltage, 1mL/h injection speed, 15G flat head needle with needle specification and 15cm distance between the needle and a receiver, so as to obtain the composite fiber membrane patch.
Fig. 3 is an experimental view after 24d of peritoneal defect repair using the composite fiber membrane patch provided in this comparative example. As can be seen from the figure, the composite fiber membrane patch was severely adhered to the peritoneum.
Comparative example 2.
This comparative example a composite fiber membrane patch was prepared by the method of example 1, except that the heptadecafluorononyl- (4-hydroxybutyrate) block copolymer was replaced with an equivalent amount of poly (4-hydroxybutyrate) in the composite fiber membrane patch, with the same other conditions as in example 1.
Comparative example 3.
The comparative example used the method of example 1 to prepare a composite fiber membrane patch, except that the composite fiber membrane patch did not contain perfluorodecalin, i.e., the final product, a composite fiber membrane patch, was electrospun, under otherwise identical conditions to example 1.
Test cases.
The following test was conducted on the composite cellulose films of examples 1 to 3 and comparative examples 1 to 3, and the test results are shown in table 1.
(1) Tensile strength: testing according to the standard of FZ/T01034-2008;
(2) Antiblocking properties: healthy rats are selected as abdominal cavity injury test objects, the male and female parts are half, the body weight is about 200g, scratch treatment is carried out on the abdominal membrane on the right side of the abdomen of the mice, a composite fiber membrane patch is placed on the local surface of a wound for application, the abdomen is closed by continuous suturing, penicillin is anti-inflammatory after operation for 3 days, the rats are killed after operation for 1d, 7d and 14d, the wound adhesion condition of the rats is observed and tested, and the scoring is carried out by adopting the guidelines of the animal experiment examination and guide principle of the abdominal cavity internal hernia repair patch issued by the International pharmaceutical administration.
Table 1.
As shown by test results, compared with comparative examples 1-3, the tensile strength of the composite cellulose films provided by examples 1-3 is more than 32.1MPa, and the strength requirement of the abdominal wall defect repair patch is met; meanwhile, the composite cellulose membranes provided in examples 1 to 3 have low adhesion degree after being implanted into the abdominal cavity of a mouse for 4 weeks, and have excellent anti-adhesion property.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (10)
1. A composite fibrous membrane patch, characterized by: comprises 45 to 94.9 weight percent of poly (4-hydroxybutyrate), 0.001 to 50 weight percent of organic fluorine-poly (4-hydroxybutyrate) block copolymer and 5 to 20 weight percent of fluorine oil.
2. The composite fiber membrane patch of claim 1, wherein: the poly (4-hydroxybutyrate) had a weight average molecular weight of 100000 ～ 300000.
3. The composite fiber membrane patch of claim 1, wherein: the organic fluoro-poly (4-hydroxybutyrate) block copolymer is selected from one or more of a nonafluoropentyl-poly (4-hydroxybutyrate) block copolymer, a trideceth-fluorooctyl-poly (4-hydroxybutyrate) block copolymer, a heptadecafluorononyl-poly (4-hydroxybutyrate) block copolymer, a hexafluorobutyl-poly (4-hydroxybutyrate) block copolymer, a dodecafluoroheptyl-poly (4-hydroxybutyrate) block copolymer, and an octafluoropentyl-poly (4-hydroxybutyrate) block copolymer.
4. A composite fiber membrane patch according to claim 3, wherein: the preparation method of the organic fluorine-poly (4-hydroxybutyrate) block copolymer comprises the following steps: mixing organic fluoric acid and poly (4-hydroxybutyrate) with hydroxyl group at single end according to the molar input ratio of (1.0-1.5), adding tetrabutyl titanate as catalyst, heating to 150-170 ℃ under stirring, reacting for 10-14 h, and purifying to obtain the organic fluoric-poly (4-hydroxybutyrate) block copolymer.
5. The composite fiber membrane patch of claim 1, wherein: the fluorine oil is selected from one or more of perfluoro (2-n-butyl tetrahydrofuran), perfluoro tributylamine, perfluoro decalin, perfluoro methyl decalin, perfluoro tripropylamine and perfluoro polyether.
6. A method of making a composite fibrous membrane patch according to any one of claims 1 to 5, characterized by: and uniformly mixing the poly (4-hydroxybutyrate) and the organic fluorine-poly (4-hydroxybutyrate) block copolymer, spinning to obtain a prefabricated film, and pouring fluorine oil into the prefabricated film to obtain the composite fiber film patch.
7. The method of making a composite fiber membrane patch of claim 6, wherein: the spinning is one or more of melt spinning, solution spinning and electrostatic solution spinning.
8. The method of making a composite fiber membrane patch of claim 6, wherein: the perfusion method comprises the following steps: the fluorine oil is supported on the inside and the surface of the prefabricated film by a soaking and/or coating mode.
9. An anti-blocking film, characterized in that: at least comprising a composite fibre membrane patch according to any one of claims 1 to 5.
10. The anti-blocking film according to claim 9, characterized in that: the anti-adhesion membrane also comprises one or more of an anticancer drug, an anti-inflammatory drug and an anti-adhesion drug.
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