CN117004204B - Medical biodegradable microsphere and preparation process thereof - Google Patents
Medical biodegradable microsphere and preparation process thereof Download PDFInfo
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- CN117004204B CN117004204B CN202310977982.9A CN202310977982A CN117004204B CN 117004204 B CN117004204 B CN 117004204B CN 202310977982 A CN202310977982 A CN 202310977982A CN 117004204 B CN117004204 B CN 117004204B
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- butyrolactone
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- polylactic acid
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- propylene oxide
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- 239000004005 microsphere Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000003607 modifier Substances 0.000 claims abstract description 55
- 239000004626 polylactic acid Substances 0.000 claims abstract description 41
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 40
- 229930188620 butyrolactone Natural products 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006065 biodegradation reaction Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000005406 washing Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000013267 controlled drug release Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Medicinal Preparation (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses medical biodegradable microspheres, and belongs to the technical field of polymer microspheres. The raw materials for preparing the medical biodegradable microsphere comprise polylactic acid and a butyrolactone modifier. The medical biodegradable microsphere takes polylactic acid as a raw material, and the butyrolactone modifier is added, so that the biodegradation rate of the obtained modified microsphere is remarkably increased. According to the preparation process of the medical biodegradable microsphere, the butyrolactone modifier is prepared by the raw materials with a specific proportion, and the butyrolactone modifier is mixed with polylactic acid to obtain the polylactic acid microsphere with good biodegradability.
Description
Technical Field
The invention belongs to the technical field of polymer microspheres, and particularly relates to a medical biodegradable microsphere and a preparation process thereof.
Background
Polymeric microspheres are common carriers for controlled drug release, and polylactic acid (PLA) is one of the common materials. The polylactic acid material is an environment-friendly material which can be completely biodegraded, the total amount of CO2 and water generated after degradation is balanced, the greenhouse effect of the atmosphere is not increased, no pollution is caused to the environment, and any toxic substance is not generated. If it flows into soil, sewage, river and sea, it can be decomposed into CO 2 and water within 3-6 months under the action of microbes such as bacteria.
The existing pure polylactic acid microsphere can be degraded, but the degradation speed is relatively slow.
Disclosure of Invention
In view of the above problems, researchers in this patent have studied to add other components to polylactic acid to promote degradation of polylactic acid.
The first aspect of the invention discloses a medical biodegradable microsphere, which is prepared from polylactic acid and a butyrolactone modifier.
In some embodiments of the present invention, the butyrolactone modifier is prepared from a feedstock comprising propylene oxide, 1, 4-butyrolactone, and CO 2.
In some embodiments of the invention, the weight of the butyrolactone modifier is 0.1-5%, preferably 1-3%, and more preferably 2% of the weight of the polylactic acid.
The second aspect of the invention discloses a preparation process of the medical biodegradable microsphere according to the first aspect, comprising the following steps:
S01, preparing a butyrolactone modifier;
s02, mixing the L-polylactic acid microspheres and the butyrolactone modifier.
In some embodiments of the invention, in S01, the ratio of propylene oxide, 1, 4-butyrolactone, and CO 2 is (50 mL): (10-30 mL): (2.0-4.5 MPa), preferably (50 mL): (15-25 mL): (3.0-3.8 MPa).
In some embodiments of the present invention, in S01, the reaction system further includes a catalyst, preferably the catalyst is a supported bimetallic PBM type catalyst, and more preferably the catalyst is used in an amount of 0.5 to 1.5g of catalyst per 50mL of propylene oxide.
In some embodiments of the invention, in S01, the reaction is performed at 100-150℃for 10-16h.
In some embodiments of the invention, the step of washing the copolymer with an ethanol solution of hydrochloric acid, preferably with 3-8% (v/v) hydrochloric acid, is further included in S01.
In some embodiments of the invention, in S02, the left-handed polylactic acid microspheres and the butyrolactone modifier are mixed, mixed in a torque rheometer for 8-15 minutes at a mixing speed of 50-100rpm and in three temperature ranges of 150-200 ℃.
In some embodiments of the present invention, in S02, a pretreatment step of drying the l-polylactic acid microspheres and the butyrolactone modifier is further included, preferably the pretreatment step is vacuum drying at 75 to 85 ℃ for 4 to 8 hours.
The beneficial effects are that:
the medical biodegradable microsphere takes polylactic acid as a raw material, and the butyrolactone modifier is added, so that the biodegradation rate of the obtained modified microsphere is remarkably increased.
According to the preparation process of the medical biodegradable microsphere, the butyrolactone modifier is prepared by the raw materials with a specific proportion, and the butyrolactone modifier is mixed with polylactic acid to obtain the polylactic acid microsphere with good biodegradability.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The raw materials, instruments and equipment of the examples and comparative examples are commercially available, and the L-polylactic acid is purchased from Wuhan mountain technology Co., ltd, and has a diameter of 5 to 25. Mu.m. The examples and comparative examples are parallel runs of the same components, component contents, preparation steps, preparation parameters, unless otherwise specified. The solvent volatilizing process of preparing microsphere includes dissolving in dichloromethane, dropping into deionized water containing sodium dodecyl benzene sulfonate slowly, stirring, heating to volatilize dichloromethane, centrifuging, washing and drying to obtain microsphere of 20-25 micron diameter.
Example 1
A preparation process of medical biodegradable microspheres comprises the following steps:
(1) Preparation of butyrolactone modifier
After nitrogen purging for 5min, adding 1g of supported bimetallic PBM catalyst, 50mL of propylene oxide, 50mL of benzene and 20mL of 1, 4-butyrolactone into a reactor, fully and uniformly stirring, reacting for 12h at 120 ℃ under the pressure of 3.5MPa by CO 2, cooling, removing residual gas, washing the copolymer by using ethanol solution of 5% (v/v) hydrochloric acid, and drying to obtain a modifier;
(2) Taking the L-polylactic acid microspheres and the butyrolactone modifier, drying in vacuum for 6 hours at 80 ℃, mixing in a torque rheometer for 10 minutes, wherein the mixing speed is 60rpm, the three-stage temperature areas are 180 ℃, and the addition amount of the modifier is 2% (w/w) of the L-polylactic acid microspheres. And then preparing the microspheres by a solvent volatilization method.
Example 2
A preparation process of medical biodegradable microspheres comprises the following steps:
(1) Preparation of butyrolactone modifier
After nitrogen purging for 5min, adding 1g of supported bimetallic PBM catalyst, 50mL of propylene oxide, 50mL of benzene and 20mL of 1, 4-butyrolactone into a reactor, fully and uniformly stirring, reacting for 12h at 120 ℃ under the pressure of 3.5MPa by CO 2, cooling, removing residual gas, washing the copolymer by using ethanol solution of 5% (v/v) hydrochloric acid, and drying to obtain a modifier;
(2) Taking the L-polylactic acid microspheres and the butyrolactone modifier, drying in vacuum for 6 hours at 80 ℃, mixing in a torque rheometer for 10 minutes, wherein the mixing speed is 60rpm, the three-stage temperature areas are 180 ℃, and the addition amount of the modifier is 1% (w/w) of the L-polylactic acid microspheres. And then preparing the microspheres by a solvent volatilization method.
Example 3
A preparation process of medical biodegradable microspheres comprises the following steps:
(1) Preparation of butyrolactone modifier
After nitrogen purging for 5min, adding 1g of supported bimetallic PBM catalyst, 50mL of propylene oxide, 50mL of benzene and 20mL of 1, 4-butyrolactone into a reactor, fully and uniformly stirring, reacting for 12h at 120 ℃ under the pressure of 3.5MPa by CO 2, cooling, removing residual gas, washing the copolymer by using ethanol solution of 5% (v/v) hydrochloric acid, and drying to obtain a modifier;
(2) Taking the L-polylactic acid microspheres and the butyrolactone modifier, drying in vacuum for 6 hours at 80 ℃, mixing in a torque rheometer for 10 minutes, wherein the mixing speed is 60rpm, the three-stage temperature areas are 180 ℃, and the addition amount of the modifier is 3% (w/w) of the L-polylactic acid microspheres. And then preparing the microspheres by a solvent volatilization method.
Example 4
A preparation process of medical biodegradable microspheres comprises the following steps:
(1) Preparation of butyrolactone modifier
After nitrogen purging for 5min, adding 1g of supported bimetallic PBM catalyst, 50mL of propylene oxide, 50mL of benzene and 15mL of 1, 4-butyrolactone into a reactor, fully and uniformly stirring, reacting for 12h at 120 ℃ under the pressure of 3.8MPa by CO 2, cooling, removing residual gas, washing the copolymer by using ethanol solution of 5% (v/v) hydrochloric acid, and drying to obtain a modifier;
(2) Taking the L-polylactic acid microspheres and the butyrolactone modifier, drying in vacuum for 6 hours at 80 ℃, mixing in a torque rheometer for 10 minutes, wherein the mixing speed is 60rpm, the three-stage temperature areas are 180 ℃, and the addition amount of the modifier is 2% (w/w) of the L-polylactic acid microspheres. And then preparing the microspheres by a solvent volatilization method.
Example 5
A preparation process of medical biodegradable microspheres comprises the following steps:
(1) Preparation of butyrolactone modifier
After nitrogen purging for 5min, adding 1g of supported bimetallic PBM catalyst, 50mL of propylene oxide, 50mL of benzene and 25mL of 1, 4-butyrolactone into a reactor, fully and uniformly stirring, reacting for 12h at 120 ℃ under the pressure of 3.0MPa by CO 2, cooling, removing residual gas, washing the copolymer by using an ethanol solution of 5% (v/v) hydrochloric acid, and drying to obtain a modifier;
(2) Taking the L-polylactic acid microspheres and the butyrolactone modifier, drying in vacuum for 6 hours at 80 ℃, mixing in a torque rheometer for 10 minutes, wherein the mixing speed is 60rpm, the three-stage temperature areas are 180 ℃, and the addition amount of the modifier is 2% (w/w) of the L-polylactic acid microspheres. And then preparing the microspheres by a solvent volatilization method.
Comparative example 1
A preparation process of medical biodegradable microspheres comprises the following steps:
(1) Preparation of butyrolactone modifier
After nitrogen purging for 5min, adding 1g of supported bimetallic PBM catalyst, 50mL of propylene oxide, 50mL of benzene and 20mL of 1, 4-butyrolactone into a reactor, fully and uniformly stirring, reacting for 12h at 120 ℃ under the pressure of 3.5MPa by CO 2, cooling, removing residual gas, washing the copolymer by using ethanol solution of 5% (v/v) hydrochloric acid, and drying to obtain a modifier;
(2) Taking the L-polylactic acid microspheres and the butyrolactone modifier, drying in vacuum at 80 ℃ for 6 hours, mixing in a torque rheometer for 10 minutes, wherein the mixing speed is 60rpm, the three-stage temperature areas are 180 ℃, and the addition amount of the modifier is 0.2% (w/w) of the L-polylactic acid microspheres. And then preparing the microspheres by a solvent volatilization method.
Comparative example 2
A preparation process of medical biodegradable microspheres comprises the following steps:
(1) Preparation of butyrolactone modifier
After nitrogen purging for 5min, adding 1g of supported bimetallic PBM catalyst, 50mL of propylene oxide, 50mL of benzene and 10mL of 1, 4-butyrolactone into a reactor, fully and uniformly stirring, reacting for 12h at 120 ℃ under the pressure of 3.5MPa by CO 2, cooling, removing residual gas, washing the copolymer by using ethanol solution of 5% (v/v) hydrochloric acid, and drying to obtain a modifier;
(2) Taking the L-polylactic acid microspheres and the butyrolactone modifier, drying in vacuum for 6 hours at 80 ℃, mixing in a torque rheometer for 10 minutes, wherein the mixing speed is 60rpm, the three-stage temperature areas are 180 ℃, and the addition amount of the modifier is 2% (w/w) of the L-polylactic acid microspheres. And then preparing the microspheres by a solvent volatilization method.
Comparative example 3
A preparation process of medical biodegradable microspheres comprises the following steps:
(1) Preparation of butyrolactone modifier
After nitrogen purging for 5min, adding 1g of supported bimetallic PBM catalyst, 50mL of propylene oxide, 50mL of benzene and 20mL of 1, 4-butyrolactone into a reactor, fully and uniformly stirring, reacting for 12h at 120 ℃ under the pressure of 2.0MPa by CO 2, cooling, removing residual gas, washing the copolymer by using ethanol solution of 5% (v/v) hydrochloric acid, and drying to obtain a modifier;
(2) Taking the L-polylactic acid microspheres and the butyrolactone modifier, drying in vacuum for 6 hours at 80 ℃, mixing in a torque rheometer for 10 minutes, wherein the mixing speed is 60rpm, the three-stage temperature areas are 180 ℃, and the addition amount of the modifier is 2% (w/w) of the L-polylactic acid microspheres. And then preparing the microspheres by a solvent volatilization method.
Experimental example degradation Properties
The medical biodegradable microspheres and the untreated polylactic acid microspheres were obtained in the examples and comparative examples, dried to constant weight, buried under the soil at 0.1m, and carried out in an incubator with air and soil relative humidity of 60% and 80%, respectively. The biodegradation temperature is maintained at 25-30 ℃. Taking out the sample after 90 days, washing, and drying to constant weight. Each sample had three parallel groups and the result was the mean. 90-day weight loss ratio= (W1-W2)/w1×100%, W1 is the original weight, and W2 is the weight after 90 days of degradation. The results are shown in Table 1.
TABLE 1 degradation Properties
The results show that the degradation rates of the modified microspheres obtained in examples 1-5 are better than those of the control examples 1-3 and the blank.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the above-described embodiments and examples, and various changes may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. The medical biodegradable microsphere is characterized in that the prepared raw materials comprise the L-polylactic acid microsphere and the butyrolactone modifier, the weight of the butyrolactone modifier is 1-3% of that of the L-polylactic acid microsphere, the L-polylactic acid microsphere and the butyrolactone modifier are mixed in a torque rheometer for 8-15min, the mixing speed is 50-100rpm, and three-stage temperature ranges are 150-200 ℃ to prepare the medical biodegradable microsphere; wherein the raw materials for preparing the butyrolactone modifier comprise propylene oxide, 1, 4-butyrolactone and CO 2, and the ratio of the propylene oxide, the 1, 4-butyrolactone and the CO 2 is 50mL:15-25mL:3.0-3.8MPa, propylene oxide, 1, 4-butyrolactone and CO 2 react for 10-16h at 100-150 ℃ to prepare the butyrolactone modifier.
2. The process for preparing the medical biodegradable microspheres according to claim 1, comprising the steps of:
S01, preparing a butyrolactone modifier:
The preparation raw materials comprise propylene oxide, 1, 4-butyrolactone and CO 2, wherein the ratio of the propylene oxide to the 1, 4-butyrolactone to the CO 2 is 50mL:15-25mL:3.0-3.8MPa, and propylene oxide, 1, 4-butyrolactone and CO 2 react for 10-16h at 100-150 ℃;
s02, mixing the L-polylactic acid microspheres and the butyrolactone modifier:
The L-polylactic acid microsphere and the butyrolactone modifier are mixed in a torque rheometer for 8-15min, the mixing speed is 50-100rpm, and the three temperature ranges are 150-200 ℃.
3. The process according to claim 2, wherein in S01, the ratio of propylene oxide, 1, 4-butyrolactone and CO 2 is 50mL:15-25mL:3.0-3.8MPa.
4. The preparation process according to claim 2 or 3, wherein in S01, the reaction system further comprises a catalyst, the catalyst is a supported bimetallic PBM type catalyst, and the catalyst is used in an amount of 0.5-1.5g of catalyst per 50mL of propylene oxide.
5. A process according to claim 2 or 3, characterized in that in S01, the copolymer is washed with an ethanol solution of hydrochloric acid.
6. The process according to claim 5, wherein the ethanol solution of hydrochloric acid is an ethanol solution of hydrochloric acid having a volume concentration of 3 to 8%.
7. The preparation process according to claim 2 or 3, wherein in S02, a pretreatment step of drying the l-polylactic acid microspheres and the butyrolactone modifier is further included.
8. The preparation process according to claim 7, wherein the pretreatment step is vacuum drying at 75-85 ℃ for 4-8 hours.
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