CN113174021A - Photosensitive bioabsorbable polymer with in-situ anti-cell adhesion function and preparation method thereof - Google Patents
Photosensitive bioabsorbable polymer with in-situ anti-cell adhesion function and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
-
- 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
- A61L31/04—Macromolecular materials
- A61L31/048—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- A61L31/14—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- General Health & Medical Sciences (AREA)
- Surgery (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention discloses a photosensitive bioabsorbable polymer with an in-situ anti-cell adhesion function and a preparation method thereof, belonging to the technical field of biomedical high molecular materials and photocuring, wherein the photosensitive bioabsorbable polymer comprises the following raw materials: multi-arm lactic acid oligomer with double bonds, vinyl pyrrolidone and photoinitiator; according to the invention, NVP with the cell adhesion resisting effect is added into the multi-arm lactic acid oligomer liquid with a double-bond structure in situ, and then the components are subjected to cross-linking curing molding through an ultraviolet curing technology to prepare the photosensitive bioabsorbable polymer with the in-situ cell adhesion resisting function, so that the problems of easy peeling of a drug slow-release cell transitional proliferation resisting coating and sudden drug release in the traditional altering technology can be effectively solved, and the photosensitive bioabsorbable polymer has the advantages of safe preparation process, low cost, no need of solvent, high curing speed and the like.
Description
Technical Field
The invention relates to the technical field of biomedical high molecular materials and photocuring, in particular to a photosensitive bioabsorbable polymer with an in-situ anti-cell adhesion function and a preparation method thereof.
Background
The ultraviolet light curing technology (UV technology) is a technology in which a photoinitiator (or photosensitizer) is added to a system with a special formula (called a light curing system), and after high-intensity ultraviolet light generated in light curing equipment is absorbed, active free radicals or cations are generated, so that polymerization, crosslinking and grafting reactions are initiated, and the system is converted from a liquid state to a solid state within a certain time. The technology has the advantages of fast curing, high production efficiency, energy conservation, environmental protection, high quality, economy, suitability for various base materials and the like, and is widely applied to the fields of aerospace, medical treatment and health, automobile electrical appliances and the like. The ultraviolet curing system (UV system) mainly comprises three parts of photosensitive oligomer, photosensitive monomer (also called as reactive diluent) and photoinitiator. The UV system is usually in liquid form, and the performance of the UV system directly affects the performance of the molded part, while the performance of the UV system is mainly affected by the distribution ratio and performance of the components in the system.
Polylactic acid (PLA), as a bioabsorbable polyester material with good biocompatibility and mechanical properties, has been widely used to prepare various biomedical materials and devices, such as medical sutures, drug controlled release carriers, bone nails, tissue engineering scaffolds, etc. However, in the development of blood contact materials and products for a long time, although bioabsorbable vascular stents, artificial small blood vessels, and the like represented by PLA have been the focus of research in academia and industry, researchers found that such bioabsorbable materials and devices are prone to excessive proliferation of smooth muscle cells and the like on the surface after implantation and further generate inflammatory reaction in the degradation process. Therefore, researchers have attempted to alleviate the above problems by modifying the surface of such materials and devices with various coatings. However, as the PLA and the coating carrier are both made of bioabsorbable materials, the PLA and the coating carrier can be gradually degraded in a human body along with the increase of the implantation time, and the coating is easy to peel off, so that the modification of the coating fails. Therefore, it would be of great interest to provide a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function and a preparation method thereof.
Disclosure of Invention
In view of the above disadvantages or defects, the present invention provides a photosensitive bioabsorbable polymer with in-situ anti-cell adhesion function and a preparation method thereof, which can effectively solve the problems of easy peeling of a drug sustained-release anti-cell-transitional-proliferation coating and sudden drug release in the conventional modification technology, and the preparation method has the advantages of safe preparation process, low cost, no need of solvent, high curing speed, etc.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a photosensitive bioabsorbable polymer with an in-situ anti-cell adhesion function, which comprises the following raw materials: multi-arm lactic acid oligomer with double bonds, vinyl pyrrolidone and photoinitiator.
Further, the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function comprises the following raw materials in percentage by weight: 20% -90% of multi-arm lactic acid oligomer with double bonds, 9% -70% of vinyl pyrrolidone (NVP) and 1% -10% of photoinitiator.
Further, the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function comprises the following raw materials in percentage by weight: 45% -62% of multi-arm lactic acid oligomer with double bonds, 32% -50% of vinyl pyrrolidone and 4% -8% of photoinitiator.
Further, the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function comprises the following raw materials in percentage by weight: 55% of multi-arm lactic acid oligomer with double bonds, 44% of vinyl pyrrolidone and 6% of photoinitiator.
Further, the number of arms in the multi-arm type lactic acid oligomer having a double bond ranges from 2 to 20, and the polymer ranges from 5 to 50.
Further, the photoinitiator is one or more of Irgacure 2959, Irgacure 819, Irgacure 1700, and Darocure 1173.
Further, the double-bond-bearing multi-arm lactic acid oligomer comprises one or more of the following double-bond structures:
(monoethyl fumarate: FAME-),
(methacryloyl group: MC-) and
(acryloyl: AC-);
wherein R is
n is 5 to 50.
Further, the multi-arm lactic acid oligomer having a double bond is prepared by the following method:
(1) adding ethyl acetate and lactide into a round-bottom flask, building a reflux device, heating to 60-80 ℃, completely dissolving the lactide, filtering under reduced pressure, carrying out ice bath on the filtrate for 2-10h, separating out needle crystals, filtering under reduced pressure again, and drying under vacuum to obtain a purified product;
(2) adding an initiator, a catalyst and an organic solvent into the purified product obtained in the step (1), reacting for more than 24 hours at the temperature of 60-100 ℃ under the protection of nitrogen, and then sequentially carrying out reprecipitation, reduced pressure filtration and vacuum drying to obtain a lactic acid oligomerization product; wherein the organic solvent is at least one of benzene, toluene, xylene, chloroform, dichloromethane and ethyl acetate, and the initiator is at least one of glycerol, trimethylolpropane, hexanetriol, sorbitol, sucrose, xylitol and pentaerythritol;
(3) dropwise adding a modifier, a water removing agent, an acylating agent and an organic solvent into the lactic acid oligomer product obtained in the step (2), reacting at room temperature for more than 24 hours under the protection of nitrogen, and then sequentially carrying out filtration, reprecipitation, reduced pressure filtration and vacuum drying to obtain a photosensitive liquid fully-degradable oligomer capable of being rapidly subjected to photocuring molding; wherein the modifier is at least one of fumaric acid monoethyl ester, acryloyl chloride and methacryloyl chloride, and the light curing parameter is illumination intensity of 400-600mW/cm2And the time is 1-30 s.
The invention also provides a preparation method of the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function, which comprises the following steps:
step (1): uniformly mixing the raw materials of each component at normal temperature to obtain a mixture;
step (2): and (2) placing the mixture obtained in the step (1) in a forming die, uniformly infiltrating and spreading, and then transferring to ultraviolet curing equipment for carrying out photocuring reaction to prepare the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function.
Further, the light curing reaction in the step (2) is performed under the condition that the light intensity is 10-100mW/cm2The illumination time is 90-300 s.
The invention has the following advantages:
1. according to the invention, NVP with the cell adhesion resistance function is added into multi-arm lactic acid oligomer liquid with a double-bond structure in situ, and the components are further subjected to cross-linking, curing and forming through an ultraviolet curing technology, so that the photosensitive bioabsorbable polymer with the in-situ cell adhesion resistance function is prepared, and the material has a good cell adhesion resistance function for life; the NVP anti-adhesion component is added in situ and fixed in a crosslinking mode in the photopolymerization reaction process, so that the problem of functional failure caused by coating peeling does not exist, and even if the main material is a bioabsorbable component, the NVP component can be effectively released in the degradation process, so that the anti-adhesion effect can be continuously exerted. The method has the technical advantages of safe preparation process, low cost, no need of using solvent, high curing speed and the like; provides a brand new material synthesis and modification method for the problem of how to realize continuous cell adhesion proliferation resistance of the current blood contact type bioabsorbable material and apparatus for a long time;
2. the photosensitive bioabsorbable polymer provided by the invention not only effectively maintains the good bioabsorbability of the main material, but also can continuously and effectively release the anti-adhesion NVP component in the whole service period of the material, effectively reduces the implantation failure of the blood contact material and the device caused by the hyperproliferation adhesion of cells after implantation, potentially prolongs the service life of the device, and is expected to be widely applied to the development of various blood contact medical device products;
3. the photosensitive bioabsorbable polymer provided by the invention not only can be effectively cured and formed under ultraviolet illumination by virtue of double bond activity in a molecular structure, but also can fix the NVP component with excellent cell adhesion resistance in a photocrosslinking network mode, so that the cured polymer has an excellent cell adhesion resistance function; compared with the traditional surface coating anti-adhesion mode, the NVP anti-adhesion component is added and fixed in situ in the photopolymerization reaction process, so that the problem of functional failure caused by coating peeling does not exist, and even if the main material is a bioabsorbable component, the NVP component can be effectively released in the degradation process, so that the anti-adhesion effect is continuously exerted; the material can be widely applied to the development of various implantation intervention medical devices (such as a bioabsorbable vascular stent, a tracheal stent or an artificial blood vessel and the like), and endows the medical devices with excellent anti-cell adhesion function, thereby effectively keeping the material effectively preventing implantation failure caused by the excessive proliferation of various cells in a human body after being implanted into the body, and prolonging the service life of the implantation intervention medical devices.
Drawings
FIG. 1 is a schematic diagram of the preparation of a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function (taking FAME as an example);
FIG. 2 is a contact angle of the surface of a sample of a photosensitive bioabsorbable polymer with in situ anti-cell adhesion functionality prepared by the method of the invention;
FIG. 3 is a contact angle of a surface of a sample of a conventional extruded PLA material;
FIG. 4 is a fluorescence micrograph of L929 fibroblasts stained on the surface of a sample of a photosensitive bioabsorbable polymer having in situ anti-cell adhesion properties prepared by the method of the present invention, cultured for 1 day and 3 days;
FIG. 5 is a fluorescence micrograph of L929 fibroblasts stained from the surface of a sample of conventional extruded PLA material after 1 day and 3 days of culture.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are illustrative only and are not limiting upon the invention, since numerous insubstantial modifications and variations within the spirit and scope of the invention will be suggested to those skilled in the art.
Example 1
This example 1 provides a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function, and the specific formulation (100 g) is as follows:
FAME-modified three-arm photosensitive lactic acid oligomer (FAME-3arms-LAO) 45 g
NVP 55 g
Irgacure 29595 g
Wherein, the FAME (fumaric acid monoethyl ester) modified three-arm type photosensitive lactic acid oligomer (double-bond three-arm lactic acid oligomer) is prepared by the following method:
(1) sequentially adding 100g of ethyl acetate and 80g of levorotatory lactide into a round-bottom flask, and continuously refluxing and stirring at 75 ℃ until the levorotatory lactide is completely dissolved; then carrying out reduced pressure filtration on the obtained solution, and collecting filtrate; the filtrate is ice-washed for more than 5 hours until needle-shaped levorotatory lactide crystals are completely separated out; filtering under reduced pressure again, vacuum drying to obtain purified levorotatory lactide crystal, and storing in a drying oven;
(2) using glycerol as an initiator, stannous octoate as a catalyst, toluene as a solvent, nitrogen as a protective gas, reacting for 24h at 80 ℃, then re-precipitating in ethyl ether, filtering under reduced pressure, and drying under vacuum to open-loop polymerize the mixture to form a three-arm lactic acid oligomer, wherein the feeding ratio is calculated according to 6mol of levorotatory lactide corresponding to each mol of hydroxyl;
(3) using monoethyl fumarate as a modifier with double bond activity, using dicyclohexylcarbodiimide as a water removal agent, using 4-dimethylaminopyridine as an acylating agent and toluene as a solvent, and slowly dripping the mixture into a three-neck flask filled with the three-arm lactic acid oligomer synthesized in the second stage, wherein the aim is to introduce an active double bond at the molecular chain end of the oligomer; wherein, the ratio of glycerol: monoethyl fumarate: the feeding molar ratio of dicyclohexylcarbodiimide is 1: 6: 6; the whole system is in the protective atmosphere of nitrogen, and room temperature reaction is carried out; after the reaction is finished, filtering to remove generated Dicyclohexylurea (DCU), and finally re-precipitating in methanol, filtering under reduced pressure, and drying in vacuum to obtain the required photosensitive three-arm lactic acid prepolymer;
(4) pouring the oligomer into a mold with a certain shape, and placing the mold into ultraviolet curing equipment or photocuring 3D printing equipment for molding, wherein the light intensity is 400mW/cm2And the illumination time is 30s in total, so that the FAME modified three-arm photosensitive lactic acid oligomer is prepared.
The preparation method of the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function has the preparation principle schematic diagram shown in figure 1, and specifically comprises the following steps:
step (1): uniformly mixing the raw materials at normal temperature to obtain a mixture;
step (2): placing the mixture obtained in the step (1) in a forming die, soaking and spreading uniformly, and then transferring to ultraviolet curing equipment for photocuring reaction to prepare the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function; wherein the light curing reaction condition is that the light intensity is 100mW/cm2The light curing time was 120 s.
Example 2
This example 2 provides a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function, and the specific formulation (100 g) is as follows:
MC modified three-arm photosensitive lactic acid oligomer (MC-3arms-LAO) 60 g
NVP 32 g
Irgacure 29598 g
Wherein, the FAME (fumaric acid monoethyl ester) modified three-arm type photosensitive lactic acid oligomer (double-bond three-arm lactic acid oligomer) is prepared by the following method:
among them, the MC (methacryloyl chloride) -modified three-arm type photosensitive lactic acid oligomer (double bond-containing three-arm lactic acid oligomer) differs from the method for producing the FAME-modified three-arm type photosensitive lactic acid oligomer in example 1 only in that: and (4) replacing the modifier in the step (3) with methacryloyl chloride, wherein the rest steps and parameters are the same.
The preparation method of the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function specifically comprises the following steps:
step (1): uniformly mixing the raw materials of each component at normal temperature to obtain a mixture;
step (2): placing the mixture obtained in the step (1) in a forming die, soaking and spreading uniformly, and then transferring to ultraviolet curing equipment for photocuring reaction to prepare the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function; wherein the light curing reaction condition is that the light intensity is 60mW/cm2The light curing time is 300 s.
Example 3
This example 3 provides a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function, the specific formulation (100 g) is as follows:
AC-modified three-arm photosensitive lactic acid oligomer (AC-3arms-LAO) 55 g
NVP 44 g
Irgacure 29596 g
Among them, the AC (acryloyl chloride) -modified three-arm type photosensitive lactic acid oligomer (double bond-containing three-arm lactic acid oligomer) differs from the method for producing the FAME-modified three-arm type photosensitive lactic acid oligomer in example 1 only in that: and (4) replacing the modifier in the step (3) with acryloyl chloride, wherein the rest steps and parameters are the same.
(1) Sequentially adding 150g of ethyl acetate and 100g of dextro-lactide into a round-bottom flask, and continuously refluxing and stirring at 75 ℃ until the levo-lactide is completely dissolved; then carrying out reduced pressure filtration on the obtained solution, and collecting filtrate; the filtrate is iced for more than 8 hours until needle-shaped levorotatory lactide crystals are completely separated out; filtering under reduced pressure again, vacuum drying to obtain purified levorotatory lactide crystal, and storing in a drying oven;
(2) hexanetriol is used as an initiator, stannous octoate is used as a catalyst, chloroform is used as a solvent, nitrogen is used as a protective gas, the reaction is carried out for 48h at the temperature of 80 ℃, and then the precipitation is carried out again in ether, the reduced pressure filtration and the vacuum drying are carried out, so that the ring opening polymerization is carried out to form the three-arm lactic acid oligomer, wherein the feeding ratio is calculated according to the 7mol of D-lactide corresponding to each mol of hydroxyl.
(3) Using acryloyl chloride as a modifier with double bond activity, using dicyclohexylcarbodiimide as a water removal agent, using 4-dimethylaminopyridine as an acylating agent and chloroform as a solvent, and slowly dripping the modified product into a three-neck flask filled with the three-arm lactic acid oligomer synthesized in the second stage, wherein the aim is to introduce an active double bond at the molecular chain end of the oligomer; wherein, pentaerythritol: acryloyl chloride: the feeding molar ratio of dicyclohexylcarbodiimide is 1: 7: 7; the whole system is in the protective atmosphere of nitrogen, and room temperature reaction is carried out; after the reaction is finished, filtering to remove generated Dicyclohexylurea (DCU), finally re-precipitating in methanol, filtering under reduced pressure, and drying in vacuum to obtain the required photosensitive quadriarmed lactic acid prepolymer;
(4) pouring the oligomer into a mold, and placing the mold into ultraviolet curing equipment or photocuring 3D printing equipment for molding, wherein the light intensity is 600mW/cm2And the illumination time is 8s in total, and the AC modified three-arm photosensitive lactic acid oligomer is prepared.
The preparation method of the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function specifically comprises the following steps:
step (1): uniformly mixing the raw materials of each component at normal temperature to obtain a mixture;
step (2): placing the mixture obtained in the step (1) in a forming die, soaking and spreading uniformly, and then transferring to ultraviolet curing equipment for photocuring reaction to prepare the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function; wherein the light curing reaction condition is that the light intensity is 50mW/cm2The light curing time is 300 s.
Example 4
This example 4 provides a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function, and the specific formulation (100 g) is as follows:
FAME-modified six-arm photosensitive lactic acid oligomer (FAME-6arms-LAO) 66 g
NVP 27 g
Irgacure 29597 g
Among them, the FAME-modified six-arm photosensitive lactic acid oligomer (double-bond-containing multi-arm lactic acid oligomer) differs from the method for preparing the FAME-modified three-arm photosensitive lactic acid oligomer in example 1 only in that: and (3) replacing initiator hexanetriol in the step (2) with sorbitol, wherein the rest steps and parameters are the same.
The preparation method of the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function specifically comprises the following steps:
step (1): uniformly mixing the raw materials of each component at normal temperature to obtain a mixture;
step (2): placing the mixture obtained in the step (1) in a forming die, soaking and spreading uniformly, and then transferring to ultraviolet curing equipment for photocuring reaction to prepare the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function; wherein the light curing reaction condition is that the light intensity is 100mW/cm2The light curing time was 90 s.
Example 5
This example 5 provides a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function, and the specific formulation (100 g) is as follows:
MC-modified eight-arm photosensitive lactic acid oligomer (MC-6arms-LAO) 66 g
NVP 31 g
Irgacure 29599 g
The preparation method of the MC-modified eight-arm photosensitive lactic acid oligomer differs from the FAME-modified three-arm photosensitive lactic acid oligomer in example 1 only in that: replacing initiator hexanetriol in the step (2) with cane sugar (8-membered alcohol), replacing the modifier in the step (3) with methacryloyl chloride, and keeping the same steps and parameters.
The preparation method of the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function specifically comprises the following steps:
step (1): uniformly mixing the raw materials of each component at normal temperature to obtain a mixture;
step (2): placing the mixture obtained in the step (1) in a forming die, soaking and spreading uniformly, and then transferring to ultraviolet curing equipment for photocuring reaction to prepare the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function; wherein the light curing reaction condition is that the light intensity is 80mW/cm2The light curing time was 120 s.
Example 6
This example 6 provides a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function, and the specific formulation (100 g) is as follows:
AC-modified five-arm photosensitive lactic acid oligomer (AC-6arms-LAO) 55 g
NVP 41 g
Irgacure 29594 g
Among them, the AC (acryloyl chloride) -modified five-arm type photosensitive lactic acid oligomer (double bond-containing three-arm lactic acid oligomer) differs from the method for producing the FAME-modified three-arm type photosensitive lactic acid oligomer in example 1 only in that: replacing initiator hexanetriol in the step (2) with xylitol, replacing modifier in the step (3) with acryloyl chloride, and keeping the same steps and parameters.
The preparation method of the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function specifically comprises the following steps:
step (1): uniformly mixing the raw materials of each component at normal temperature to obtain a mixture;
step (2): placing the mixture obtained in the step (1) in a forming die, soaking and spreading uniformly, and then transferring to ultraviolet curing equipment for photocuring reaction to prepare the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function; wherein the light intensity of the photocuring reaction condition is 70mW/cm2The light curing time was 150 s.
Examples of the experiments
The photosensitive bioabsorbable polymer obtained in example 1 above was subjected to contact angle test and mouse fibroblast (L929) culture for a certain period of time and photographed by microscope correspondingly, and the test results are shown in FIGS. 2 to 5. The contact angle of the surface of the sample of the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function prepared by the invention in the figure 2 is 75 +/-5 degrees, the contact angle of the surface of the sample of the traditional extrusion forming PLA material in the figure 3 is 91 +/-2 degrees, and the comparison of fluorescence micrographs in the figures 4-5 shows that the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function prepared by the invention has the excellent anti-cell adhesion function.
The foregoing is merely exemplary and illustrative of the present invention and it is within the purview of one skilled in the art to modify or supplement the embodiments described or to substitute similar ones without the exercise of inventive faculty, and still fall within the scope of the claims.
Claims (9)
1. A photosensitive bioabsorbable polymer with in-situ anti-cell adhesion function is characterized by comprising the following raw materials: multi-arm lactic acid oligomer with double bonds, vinyl pyrrolidone and photoinitiator.
2. The photosensitive bioabsorbable polymer with in situ anti-cell adhesion function of claim 1, comprising the following raw materials in weight percent: 20-90% of multi-arm lactic acid oligomer with double bonds, 9-70% of vinyl pyrrolidone and 1-10% of photoinitiator.
3. The photosensitive bioabsorbable polymer with in situ anti-cell adhesion function of claim 2, comprising the following raw materials in weight percent: 45% -62% of multi-arm lactic acid oligomer with double bonds, 32% -50% of vinyl pyrrolidone and 4% -8% of photoinitiator.
4. The photosensitive bioabsorbable polymer with in situ anti-cell adhesion function of claim 3, comprising the following raw materials in weight percent: 55% of multi-arm lactic acid oligomer with double bonds, 44% of vinyl pyrrolidone and 6% of photoinitiator.
5. The photosensitive bioabsorbable polymer with in situ anti-cell adhesion function of any of claims 1-4, wherein the number of arms in the double-bonded multi-arm lactic acid oligomer ranges from 2 to 20.
6. The photosensitive bioabsorbable polymer with in situ anti-cell adhesion function of any of claims 1-4, wherein the double-bonded multi-arm lactic acid oligomer comprises one or more of the following double bond structures:
wherein R is
n is 5 to 50.
7. The photosensitive bioabsorbable polymer with in situ cell adhesion resistance of any of claims 1-4, wherein the photoinitiator is one or more of Irgacure 2959, Irgacure 819, Irgacure 1700 and Darocure 1173.
8. The method for preparing a photosensitive bioabsorbable polymer with in situ anti-cell adhesion function according to any of claims 1 to 7, comprising the steps of:
step (1): uniformly mixing the raw materials at normal temperature to obtain a mixture;
step (2): and (2) placing the mixture obtained in the step (1) in a forming die, infiltrating and uniformly spreading the mixture, and then transferring the mixture to ultraviolet curing equipment for carrying out photocuring reaction to prepare the photosensitive bioabsorbable polymer with the in-situ anti-cell adhesion function.
9. The method for preparing the photosensitive bioabsorbable polymer having the in situ anti-cell adhesion function according to claim 8, wherein the photocuring reaction in the step (2) is performed under the condition of light intensity of 10-100mW/cm2The illumination time is 90-300 s.
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