CN113354823A - Block polymer for full-degradable vascular stent and preparation method thereof - Google Patents
Block polymer for full-degradable vascular stent and preparation method thereof Download PDFInfo
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- CN113354823A CN113354823A CN202110678348.6A CN202110678348A CN113354823A CN 113354823 A CN113354823 A CN 113354823A CN 202110678348 A CN202110678348 A CN 202110678348A CN 113354823 A CN113354823 A CN 113354823A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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
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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
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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
- A61L31/14—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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Abstract
The invention discloses a block polymer for a fully degradable vascular stent and a preparation method thereof, and the block polymer comprises the following steps: step 1: the hydroxyl end group in the polylactic acid reacts with carbonyldiimidazole in a solvent to obtain the polylactic acid with the end group of carbonylimidazole; step 2: reacting the polylactic acid with the end group of carbonyl imidazole and the polymer with the end group of hydroxyl, which are obtained in the step 1, in a solvent to obtain a block polymer with a linking site of carbonate; the invention provides a method for quickly and efficiently constructing a block polymer through the special reactivity of carbonyl diimidazole, and can realize the efficient coupling of two polymers with hydroxyl functional end groups under mild conditions, thereby forming a block copolymer with a definite molecular structure; the block polymer has a definite structure, and various performances such as degradation, toughness and the like of a target polymer are more effectively improved through fine adjustment of various polymer blocks.
Description
Technical Field
The invention relates to the field of medical materials and medical instruments, in particular to a block polymer for a fully degradable vascular stent and a preparation method thereof.
Background
At present, vascular stent implantation has become one of the most effective means for treating coronary heart disease. The traditional stent product is a non-degradable metal-based drug-coated stent, and the non-degradable material of the stent is easily subjected to late thrombosis and complications caused by permanent stent retention due to poor matching of the non-degradable material with surrounding histochemical composition, physical structure and mechanical properties. The fully degradable polymer stent can be gradually degraded to be completely absorbed, so that a series of adverse events caused by permanent retention of the metal stent can be theoretically avoided. Therefore, the development of fully degradable vascular stents based on polymeric materials has become a necessary trend in the development of vascular stents.
The polylactic acid material not only has relatively high mechanical strength, but also can be gradually metabolized into lactic acid micromolecules in vivo and further decomposed into carbon dioxide and water, and has good biocompatibility. However, conventional polylactic acid materials also have some disadvantages, such as the material itself is very brittle, resulting in the risk of breakage of the stent after implantation. Polylactic acid has a relatively rigid molecular chain and almost no long-chain branches, resulting in low melt strength, which causes many difficulties in melt extrusion processing of the scaffold.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a block polymer with dual adjustable degradation performance and mechanical property for a fully degradable vascular stent and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of a block polymer for a fully degradable vascular stent comprises the following steps:
step 1: the hydroxyl end group in the polylactic acid reacts with carbonyldiimidazole in a solvent to obtain the polylactic acid with the end group of carbonylimidazole;
step 2: and (2) reacting the polylactic acid with the end group of carbonyl imidazole and the polymer with the end group of hydroxyl, which are obtained in the step (1), in a solvent to obtain the block polymer with the linkage site of carbonate.
Further, the molar ratio of the hydroxyl end group to the carbonyldiimidazole in the polylactic acid in the step 1 is 1: 1-1: 5.
Further, the reaction temperature in the step 1 is between room temperature and 100 ℃, and the reaction time is between 5 and 24 hours.
Further, the polymer with the hydroxyl end group is one of polycaprolactone, polytrimethylene carbonate and polydioxanone.
Further, the molar ratio of the polylactic acid with carbonyl imidazole as an end group to the polymer with hydroxyl as an end group in the step 2 is 1: 1-10: 1.
Further, the reaction temperature of the step 2 is room temperature-150 ℃, and the reaction time is 5 h-48 h.
Further, the solvent is one or a mixture of two or more of chloroform, dichloromethane, tetrahydrofuran, hexafluoroisopropanol and acetone in any proportion.
Further, after the reaction of the step 1 and the step 2 is completed, the purification is performed, and the purification process is as follows:
pouring the reaction solution into anhydrous ether or anhydrous methanol, carrying out suction filtration to obtain a target polymer, and then further purifying the target polymer;
the purification process is as follows:
dissolving a target polymer in a solvent, precipitating in excessive anhydrous methanol or anhydrous ether, filtering, and vacuum drying; the purification process was repeated N times.
Further, the mass concentration of the polylactic acid in the solvent in the step 1 is 0.2 g/mL-5 g/mL; the mass concentration of the polymer with the hydroxyl end group in the solvent is 0.1 g/mL-10 g/mL.
A block polymer for fully degrading a vascular stent is disclosed, wherein the polymer with the hydroxyl end group is one of polycaprolactone, polytrimethylene carbonate and polydioxanone; the obtained block polymer is one of polylactic acid-polycaprolactone PLA-PCL, polylactic acid-polytrimethylene carbonate PLA-PTMC and polylactic acid-polydioxanone PLA-PDO correspondingly;
the structure is as follows:
wherein the molecular weight of the polylactic acid is 5-30 ten thousand, the molecular weight of the polycaprolactone is 1000-5 ten thousand, the molecular weight of the polytrimethylene carbonate is 1000-5 ten thousand, and the molecular weight of the polydioxanone is 1000-5 ten thousand.
The invention has the beneficial effects that:
(1) the block polymer for the fully degradable vascular stent obtained by the invention has the performance of dual adjustability of degradation performance and mechanical property;
(2) the invention provides a method for quickly and efficiently constructing a block polymer through the special reactivity of carbonyl diimidazole, and can realize the efficient coupling of two polymers with hydroxyl functional end groups under mild conditions, thereby forming a block copolymer with a definite molecular structure;
(3) the block polymer for the fully degradable vascular stent obtained by the invention has a definite structure, and various performances such as degradation, toughness and the like of a target polymer are more effectively improved through fine adjustment of polymer blocks.
Drawings
FIG. 1 is a diagram of the synthetic scheme of the block polymer of interest according to the present invention.
FIG. 2 shows the structure of a block polymer of interest obtained by the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
A preparation method of a block polymer for a fully degradable vascular stent comprises the following steps:
step 1: hydroxyl end groups in the polylactic acid react with Carbonyldiimidazole (CDI) in a solvent to obtain polylactic acid (PLA-CDI) with carbonyl imidazole as an end group; the molar ratio of the hydroxyl end group to the carbonyldiimidazole in the polylactic acid is 1: 1-1: 5. The reaction temperature is between room temperature and 100 ℃, and the reaction time is between 5 and 24 hours. The mass concentration of the polylactic acid in the solvent is 0.2 g/mL-5 g/mL. The reaction solvent is one or a mixture of two or more of chloroform, dichloromethane, tetrahydrofuran, hexafluoroisopropanol and acetone in any proportion.
The purification process after the reaction is completed is as follows:
pouring the reaction solution into anhydrous ether or anhydrous methanol, carrying out suction filtration to obtain a target polymer, and then further purifying the target polymer;
the purification process is as follows:
dissolving the target polymer in a solvent (chloroform), precipitating in excessive anhydrous methanol or anhydrous ether, filtering, and vacuum drying; the purification process was repeated N times. The ratio of chloroform to ether or methanol is preferably 1:5, and the target product is subjected to the above dissolution precipitation process three times in order to effectively remove the impurities remaining in the product.
Step 2: and (2) reacting the polylactic acid with the end group of carbonyl imidazole and the polymer with the end group of hydroxyl, which are obtained in the step (1), in a solvent to obtain the block polymer with the linkage site of carbonate. The polymer with the hydroxyl end group is one of polycaprolactone, polytrimethylene carbonate and polydioxanone; the obtained block polymers are polylactic acid-polycaprolactone (PLA-PCL), polylactic acid-polytrimethylene carbonate (PLA-PTMC) and polylactic acid-polydioxanone (PLA-PDO), respectively. The molar ratio of the polylactic acid with the end group of carbonyl imidazole to the polymer with the end group of hydroxyl is 1: 1-10: 1. The reaction temperature is between room temperature and 150 ℃, and the reaction time is between 5 and 48 hours. The mass concentration of the polymer with the hydroxyl end group in the solvent is 0.1 g/mL-10 g/mL. The solvent is one or a mixture of two or more of chloroform, dichloromethane, tetrahydrofuran, hexafluoroisopropanol and acetone in any proportion.
The purification process after the reaction is completed is as follows:
pouring the reaction solution into anhydrous ether or anhydrous methanol, carrying out suction filtration to obtain a target polymer, and then further purifying the target polymer;
the purification process is as follows:
dissolving the target polymer in a solvent (chloroform), precipitating in excessive anhydrous methanol or anhydrous ether, filtering, and vacuum drying; the purification process was repeated N times. The ratio of chloroform to ether or methanol is preferably 1:5, and the target product is subjected to the above dissolution precipitation process three times in order to effectively remove the impurities remaining in the product.
The reaction scheme is shown in figure 1,
a block polymer for fully degrading a vascular stent is disclosed, wherein the polymer with the hydroxyl end group is one of polycaprolactone, polytrimethylene carbonate and polydioxanone; the obtained block polymer is one of polylactic acid-polycaprolactone PLA-PCL, polylactic acid-polytrimethylene carbonate PLA-PTMC and polylactic acid-polydioxanone PLA-PDO correspondingly;
the structure is as follows:
wherein the molecular weight of the polylactic acid is 5-30 ten thousand, the molecular weight of the polycaprolactone is 1000-5 ten thousand, the molecular weight of the polytrimethylene carbonate is 1000-5 ten thousand, and the molecular weight of the polydioxanone is 1000-5 ten thousand.
Example 1
A block polymer for a fully degradable vascular stent is prepared according to the following steps:
step 1: polylactic acid (Mw 50000) was reacted with carbonyldiimidazole in chloroform solution at room temperature for 24h to obtain a polylactic acid material terminated with carbonylimidazole. The mass concentration of the polylactic acid is 1 g/mL.
Wherein the molar ratio of the hydroxyl of the polylactic acid to the carbonyldiimidazole is 1:1, the solvent is concentrated and poured into anhydrous methanol, and the polylactic acid material with the target end group of the carbonyldiimidazole is obtained by suction filtration.
Step 2: polylactic acid of carbonyl imidazole and polycaprolactone (Mw ═ 1000) were reacted in a chloroform solution at 50 ℃ for 48 hours to obtain a polylactic acid-polycaprolactone block polymer having a linkage site of carbonate. Wherein the mass concentration of the polylactic acid of the carbonyl imidazole is 3 g/mL. The molar ratio of polylactic acid to polycaprolactone is 1:1, the solvent is concentrated, poured into anhydrous ether, and filtered to obtain the target block polymer material.
Compared with the conventional polylactic acid material with the same molecular weight, the block polymer material obtained by the embodiment has the advantages that the processing temperature is reduced by 10 ℃, the toughness is improved by 20%, and the degradation rate is improved by 25% as shown by a simulation liquid degradation experiment result at 37 ℃.
Example 2
A block polymer for a fully degradable vascular stent is prepared according to the following steps:
step 1: polylactic acid (Mw ═ 80000) was reacted with carbonyldiimidazole in chloroform solution for 24h at room temperature to obtain a polylactic acid material terminated with carbonylimidazole. The mass concentration of polylactic acid is 0.5 g/mL.
Wherein the molar ratio of the hydroxyl of the polylactic acid to the carbonyldiimidazole is 1:3, the solvent is concentrated and poured into anhydrous methanol, and the polylactic acid material with the target end group of the carbonyldiimidazole is obtained by suction filtration.
Step 2: polylactic acid of carbonyl imidazole and polycaprolactone (Mw ═ 2000) were reacted in a chloroform solution at 80 ℃ for 48 hours to obtain a polylactic acid-polycaprolactone block polymer having a linkage site of carbonate. Wherein the mass concentration of the polylactic acid of the carbonyl imidazole is 1 g/mL. The molar ratio of polylactic acid to polycaprolactone is 1:1, the solvent is concentrated, poured into anhydrous ether, and filtered to obtain the target block polymer material.
Compared with the conventional polylactic acid material with the same molecular weight, the block polymer material obtained by the embodiment has the advantages that the processing temperature is reduced by 12 ℃, the toughness is improved by 23%, and the degradation rate is improved by 30% as shown by a simulation liquid degradation experiment result at 37 ℃.
Example 3
A block polymer for a fully degradable vascular stent is prepared according to the following steps:
step 1: polylactic acid (Mw 100000) was reacted with carbonyldiimidazole in chloroform solution at room temperature for 48h to obtain a polylactic acid material terminated with carbonylimidazole. The mass concentration of polylactic acid is 0.1 g/mL.
Wherein the molar ratio of the hydroxyl of the polylactic acid to the carbonyldiimidazole is 1:2, the solvent is concentrated and poured into anhydrous methanol, and the polylactic acid material with the target end group of the carbonyldiimidazole is obtained by suction filtration.
Step 2: polylactic acid of carbonyl imidazole and polycaprolactone (Mw ═ 1000) were reacted in a chloroform solution at 80 ℃ for 48 hours to obtain a polylactic acid-polycaprolactone block polymer having a linkage site of carbonate. Wherein the mass concentration of the polylactic acid of the carbonyl imidazole is 1 g/mL. The molar ratio of polylactic acid to polycaprolactone is 1:1, the solvent is concentrated, poured into anhydrous ether, and filtered to obtain the target block polymer material.
Compared with the conventional polylactic acid material with the same molecular weight, the block polymer material obtained by the embodiment has the advantages that the processing temperature is reduced by 12 ℃, the toughness is improved by 23%, and the degradation rate is improved by 25% as shown by a simulation liquid degradation experiment result at 37 ℃.
Example 4
A block polymer for a fully degradable vascular stent is prepared according to the following steps:
step 1: polylactic acid (Mw ═ 80000) was reacted with carbonyldiimidazole in chloroform solution for 24h at room temperature to obtain a polylactic acid material terminated with carbonylimidazole. The mass concentration of polylactic acid is 0.5 g/mL.
Wherein the molar ratio of the hydroxyl of the polylactic acid to the carbonyldiimidazole is 1:3, the solvent is concentrated and poured into anhydrous methanol, and the polylactic acid material with the target end group of the carbonyldiimidazole is obtained by suction filtration.
Step 2: polylactic acid of carbonyl imidazole and polytrimethylene carbonate (Mw ═ 4000) were reacted in a chloroform solution at room temperature for 48 hours to obtain a polylactic acid-polycaprolactone block polymer having a linkage site of carbonate. Wherein the mass concentration of the polylactic acid of the carbonyl imidazole is 1 g/mL. The molar ratio of polylactic acid to polycaprolactone is 1:1, the solvent is concentrated, poured into anhydrous ether, and filtered to obtain the target block polymer material.
Compared with the conventional polylactic acid material with the same molecular weight, the block polymer material obtained by the embodiment has the advantages that the processing temperature is reduced by 15 ℃, the toughness is improved by 25%, and the degradation rate is improved by 36% as shown by a simulation liquid degradation experiment result at 37 ℃.
Example 5
A block polymer for a fully degradable vascular stent is prepared according to the following steps:
step 1: polylactic acid (Mw ═ 80000) was reacted with carbonyldiimidazole in chloroform solution for 24h at room temperature to obtain a polylactic acid material terminated with carbonylimidazole. The mass concentration of polylactic acid is 0.5 g/mL.
Wherein the molar ratio of the hydroxyl of the polylactic acid to the carbonyldiimidazole is 1:3, the solvent is concentrated and poured into anhydrous methanol, and the polylactic acid material with the target end group of the carbonyldiimidazole is obtained by suction filtration.
Step 2: polylactic acid of carbonyl imidazole and polydioxanone (Mw ═ 4000) were reacted in a chloroform solution at 40 ℃ for 48 hours to obtain a polylactic acid-polycaprolactone block polymer having a linkage site of a carbonate. Wherein the mass concentration of the polylactic acid of the carbonyl imidazole is 13 g/mL. The molar ratio of polylactic acid to polycaprolactone is 1:1, the solvent is concentrated, poured into anhydrous ether, and filtered to obtain the target block polymer material.
Compared with the conventional polylactic acid material with the same molecular weight, the block polymer material obtained by the embodiment has the advantages that the processing temperature is reduced by 25 ℃, the toughness is improved by 30 percent, and the degradation rate is improved by 45 percent as shown by a simulation liquid degradation experiment result at 37 ℃.
The block polymer obtained by the invention has excellent degradation performance and mechanical property, can effectively improve the comprehensive performance of the fully-degradable intravascular stent, and further improves the life quality of patients. The existing polylactic acid-polytrimethylene carbonate, polylactic acid-polycaprolactone and polylactic acid-polydioxanone are all random copolymers. The preparation method of the invention provides a block copolymer with a definite structure through the special reactivity of carbonyl diimidazole, and the block copolymer is quickly and efficiently constructed. The method can realize the high-efficiency coupling of two polymers with hydroxyl functional end groups under mild conditions to form a block copolymer with a definite molecular structure. Because the target block copolymer has a definite structure, various performances such as degradation, toughness and the like of the target polymer can be more effectively improved through fine adjustment of each polymer block.
Claims (10)
1. A preparation method of a block polymer for a fully degradable vascular stent is characterized by comprising the following steps:
step 1: the hydroxyl end group in the polylactic acid reacts with carbonyldiimidazole in a solvent to obtain the polylactic acid with the end group of carbonylimidazole;
step 2: and (2) reacting the polylactic acid with the end group of carbonyl imidazole and the polymer with the end group of hydroxyl, which are obtained in the step (1), in a solvent to obtain the block polymer with the linkage site of carbonate.
2. The preparation method of the block polymer for the fully degradable vascular stent of claim 1, wherein the molar ratio of the hydroxyl end group to the carbonyldiimidazole in the polylactic acid in the step 1 is 1: 1-1: 5.
3. The method for preparing the block polymer for the fully degradable vascular stent of claim 1, wherein the reaction temperature in the step 1 is between room temperature and 100 ℃ and the reaction time is between 5 and 24 hours.
4. The method for preparing the block polymer for the fully degradable vascular stent of claim 1, wherein the polymer with the hydroxyl end group is one of polycaprolactone, polytrimethylene carbonate and polydioxanone.
5. The method for preparing the block polymer for the fully degradable vascular stent in the claim 1, wherein the molar ratio of the polylactic acid with the carbonyl imidazole as the end group to the polymer with the hydroxyl group as the end group in the step 2 is 1: 1-10: 1.
6. The method for preparing the block polymer for the fully degradable vascular stent of claim 1, wherein the reaction temperature of the step 2 is between room temperature and 150 ℃ and the reaction time is between 5 and 48 hours.
7. The method for preparing the block polymer for the fully degradable vascular stent as claimed in claim 1, wherein the solvent is one or a mixture of two or more of chloroform, dichloromethane, tetrahydrofuran, hexafluoroisopropanol and acetone in any proportion.
8. The preparation method of the block polymer for the fully degradable vascular stent of claim 1, wherein the step 1 and the step 2 are purified after the reaction is completed, and the purification process is as follows:
pouring the reaction solution into anhydrous ether or anhydrous methanol, carrying out suction filtration to obtain a target polymer, and then further purifying the target polymer;
the purification process is as follows:
dissolving a target polymer in a solvent, precipitating in excessive anhydrous methanol or anhydrous ether, filtering, and vacuum drying; the purification process was repeated N times.
9. The method for preparing the block polymer for the fully degradable vascular stent of claim 4, wherein the mass concentration of the polylactic acid in the solvent in the step 1 is 0.2 g/mL-5 g/mL; the mass concentration of the polymer with the hydroxyl end group in the solvent is 0.1 g/mL-10 g/mL.
10. The block polymer for the fully degradable vascular stent obtained by the preparation method of any one of claims 1 to 9, wherein the polymer with the hydroxyl end group is one of polycaprolactone, polytrimethylene carbonate and polydioxanone; the obtained block polymer is one of polylactic acid-polycaprolactone PLA-PCL, polylactic acid-polytrimethylene carbonate PLA-PTMC and polylactic acid-polydioxanone PLA-PDO correspondingly;
the structure is as follows:
wherein the molecular weight of the polylactic acid is 5-30 ten thousand, the molecular weight of the polycaprolactone is 1000-5 ten thousand, the molecular weight of the polytrimethylene carbonate is 1000-5 ten thousand, and the molecular weight of the polydioxanone is 1000-5 ten thousand.
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