CN111019107A - Preparation method of multi-branched poly (glycolide-lactide) - Google Patents
Preparation method of multi-branched poly (glycolide-lactide) Download PDFInfo
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- CN111019107A CN111019107A CN201911376471.1A CN201911376471A CN111019107A CN 111019107 A CN111019107 A CN 111019107A CN 201911376471 A CN201911376471 A CN 201911376471A CN 111019107 A CN111019107 A CN 111019107A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229960001701 chloroform Drugs 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- XGMDYIYCKWMWLY-UHFFFAOYSA-N 2,2,2-trifluoroethanesulfonic acid Chemical compound OS(=O)(=O)CC(F)(F)F XGMDYIYCKWMWLY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- -1 alkyl sulfonic acid Chemical compound 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 235000015110 jellies Nutrition 0.000 description 7
- 239000008274 jelly Substances 0.000 description 7
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003937 drug carrier Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 210000000865 mononuclear phagocyte system Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003356 suture material Substances 0.000 description 1
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- 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
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
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- 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)
Abstract
The invention belongs to the technical field of organic polymer synthesis, and particularly relates to a preparation method of multi-branched-chain poly (glycolide-lactide). By adopting the invention, high-temperature reaction is avoided, energy consumption is saved, and the method is safer; the use of heavy metals is avoided; the post-treatment operation is simple, and qualified products can be obtained.
Description
Technical Field
The invention belongs to the technical field of organic polymer synthesis, and particularly relates to a preparation method of multi-branched poly (glycolide-lactide).
Background
Compared with single linear macromolecule, the multi-branched-chain macromolecule polymer can improve the physical, chemical and biological properties to a certain extent. The research shows that the multi-branched polymer has better biocompatibility in human body, larger drug loading capacity, more excellent biodegradability and better processability compared with the linear polymer. The multi-branched polymer has potential application prospect due to novel structure and unique performance.
Among various polymers, poly (lactic-co-glycolic acid) (PLGA) has good biodegradability and biocompatibility, and is widely applied to biomedical tissue engineering, such as bioabsorption suture materials, tissue engineering materials, drug controlled release systems and the like. PLGA has been approved by the FDA as one of the commonly used drug carriers due to its low toxicity. However, the straight-chain PLGA still has certain disadvantages when used as a drug carrier, is difficult to introduce a large number of functional groups, and is easily recognized and phagocytized by the reticuloendothelial system in vivo, thereby preventing the drug from reaching the target site and reducing the bioavailability of the drug. Therefore, the development of novel multi-branched PLGA has wide application prospect.
The traditional preparation method of the PLGA with the branched chains is a ring-opening polymerization method, glycolide and lactide are used as raw materials for melt polymerization, polyhydroxy compounds are used as initiators for regulating the molecular weight, and the multi-branched PLGA is synthesized at high temperature under the catalysis of heavy metal catalysts. In the method, the reaction temperature is generally above 150 ℃, most of catalysts are heavy metal catalysts, and the products are easily carbonized due to local overheating under the high-temperature condition; heavy metal catalysts accumulate in the human body to a certain extent, and cause chronic poisoning.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of multi-branched poly (glycolide-co-lactide). By adopting the invention, high-temperature reaction is avoided, energy consumption is saved, and the method is safer; the use of heavy metals is avoided; the post-treatment operation is simple, and qualified products can be obtained.
The preparation method of the multi-branched-chain poly (glycolide) provided by the invention adopts lactide monomers and glycolide monomers as raw materials, adopts Lewis acid as a catalyst, and carries out reaction at 20-30 ℃, and after the reaction is finished, the multi-branched-chain poly (glycolide) is dissolved, precipitated and dried to obtain the multi-branched-chain poly (glycolide).
The lactide monomer and the glycolide monomer are dissolved in a solvent to prepare a suspension, and the solvent is selected from dichloromethane or trichloromethane or toluene or tetrahydrofuran; after the reaction solvent is adopted, the lactide and the glycolide can be dispersed and mixed in the solvent, and the reaction temperature is reduced to a certain extent. Lactide monomer: the glycolide monomer accounts for 50: 50-85: 15.
The mass-volume ratio of the total mass of the monomers to the volume of the solvent is 1:1-1:5, the monomers comprise lactide monomers and glycolide monomers, and the unit of the mass-volume ratio is kg/L. The monomer having an excessively small proportion is not uniformly dispersed, and an excessively large proportion increases the volume of the reaction system and prolongs the reaction time.
The Lewis acid is selected from trifluoromethanesulfonic acid or trifluoroethanesulfonic acid or methanesulfonic acid or a mixture thereof, and H is extremely easy to ionize by the electron-withdrawing induction effect of the catalyst.
The dosage of the catalyst is 0.05-0.5 times of the total molar weight of the lactide monomer and the glycolide monomer, the catalyst cannot perform catalytic reaction when the proportion is too small, side reaction can be generated when the proportion is too large, and the post-treatment difficulty is increased.
The reaction time is generally 6 to 8 hours in the present invention. After the reaction is finished, jelly containing crude poly (glycolide-lactide) and unreacted monomers is obtained. Adding a benign solvent into the jelly to dissolve the jelly, then adding a poor solvent to precipitate until no precipitate is generated, separating out supernatant, adding the benign solvent and the poor solvent to precipitate, and repeatedly dissolving and precipitating for three times. The benign solvent is selected from dichloromethane or chloroform or tetrahydrofuran or toluene or xylene, and the poor solvent is selected from methanol or ethanol or n-hexane or n-heptane or diethyl ether. The mass-to-volume ratio of the total monomer mass to the benign solvent is 1-5 kg/L. The volume ratio of the benign solvent to the poor solvent is 1: 0.8-1: 2.
In conclusion, the invention prepares reactants lactide and glycolide into a suspension state by using a solvent, adopts an organic catalyst to catalyze the reaction at normal temperature to obtain a colloidal product, and then refines and dries the product by recrystallization of the organic solvent to finally obtain the target product. Compared with the prior art, the method avoids high-temperature reaction, saves energy consumption and is safer; the use of heavy metals is avoided; the post-treatment operation is simple.
Drawings
FIG. 1 is a chromatogram of the product of example 1;
FIG. 2 is a chromatogram of the product of example 2;
FIG. 3 is a chromatogram of the product of example 3;
FIG. 4 is a chromatogram of the product of example 4.
Detailed Description
Example 1
Weighing 120g of lactide monomer (LA) and 80g of glycolide monomer (GA), pouring into a three-neck flask, adding 200mL of dichloromethane, stirring, weighing 0.05 equivalent of trifluoromethanesulfonic acid and 3.0g of glycerol, adding into the three-neck flask, replacing 3 times with nitrogen, reacting at 20 ℃ for 6-8 hours to obtain a jelly, dissolving with dichloromethane, precipitating with ethanol for three times, wherein the amount of dichloromethane is 200mL each time, and the volume of ethanol is 200mL, vacuum drying is carried out until the weight is constant to obtain a finished product, the yield is 87.65%, Mw38538, Mn20640 and the viscosity is 56.79.
Example 2
Weighing 120g of lactide monomer (LA) and 80g of glycolide monomer (GA), pouring into a three-neck flask, adding 300mL of dichloromethane, stirring, weighing 0.10 equivalent of trifluoroethanesulfonic acid and 3.5g of pentaerythritol, adding into the three-neck flask, replacing with nitrogen for 3 times, reacting at 30 ℃ for 8-10 hours to obtain a jelly, dissolving with chloroform and precipitating with ethanol for three times, wherein the dosage of chloroform is 400mL each time, and vacuum drying 480mL of ethanol to constant weight to obtain the finished product, wherein the yield is 83.71%, Mw52091, Mn34697, and the viscosity is 60.16
Example 3
Weighing 140g of lactide monomer (LA) and 60g of glycolide monomer (GA), pouring into a three-neck flask, adding 800mL of chloroform, stirring, weighing 0.05 equivalent of trifluoromethanesulfonic acid and 4g of glucose, adding into the three-neck flask, replacing with nitrogen for 3 times, reacting at 25 ℃ for 8-10 hours to obtain a jelly, adding tetrahydrofuran for dissolution, precipitating with methanol for 3 times, wherein the amount of tetrahydrofuran is 600mL each time, and the amount of methanol is 480mL, and vacuum drying to constant weight to obtain a finished product, wherein the yield is 86.35%, Mw52209, Mn37745, and viscosity 70.10
Example 4
Weighing 20g of lactide monomer (LA) and 5g of glycolide monomer (GA), pouring into a three-neck flask, adding 120mL of tetrahydrofuran, stirring, weighing 0.10 equivalent of methanesulfonic acid and 0.6g of pentaerythritol, adding into the three-neck flask, performing nitrogen replacement for 3 times, reacting at 30 ℃ for 8-10 hours to obtain a jelly, dissolving with toluene, precipitating with n-hexane for three times, wherein the amount of toluene is 120mL each time, and drying with 120mL of n-hexane in vacuum to constant weight to obtain a finished product, wherein the yield is 81.23%, Mw21108, Mn14024 and viscosity is 26.7.
Claims (10)
1. A process for preparing multi-branched-chain poly (glycolide-lactide) features that the lactide monomer and glycolide monomer are used as raw materials, and the reaction is carried out at 20-30 deg.C in the presence of alkyl sulfonic acid as catalyst, and the multi-branched-chain poly (glycolide-lactide) is prepared through dissolving, depositing and drying.
2. The method for preparing multi-branched poly (glycolide-lactide) according to claim 1, wherein the lactide monomer and the glycolide monomer are dissolved in a solvent to form a suspension.
3. The method for preparing multi-branched poly (glycolide-lactide) according to claim 1, wherein the ratio of lactide monomer(s): the glycolide monomer accounts for 50: 50-85: 15.
4. The method for preparing multi-branched poly (glycolide-lactide) according to claim 2, wherein the solvent is selected from dichloromethane or trichloromethane or toluene or tetrahydrofuran, the mass-to-volume ratio of the total mass of the monomers to the volume of the solvent is 1:1-1:5, the monomers comprise lactide monomer and glycolide monomer, and the unit of the mass-to-volume ratio is kg/L.
5. The process for preparing poly-branched poly (glycolide-lactide), according to claim 2, wherein the Lewis acid is selected from the group consisting of trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, methanesulfonic acid and mixtures thereof.
6. The method of claim 2, wherein the amount of the catalyst is 0.05 to 0.5 times the total molar amount of the lactide monomer and the glycolide monomer.
7. The process according to claim 2, wherein the dissolution is carried out in a benign solvent, and the mass-to-volume ratio of the total monomer mass to the benign solvent is 1 to 5 kg/L.
8. The process according to claim 7, wherein the benign solvent is selected from dichloromethane, chloroform, tetrahydrofuran, toluene and xylene.
9. The preparation method of the multi-branched poly (glycolide-lactide) according to claim 2, wherein the poor solvent is adopted for precipitation, and the volume ratio of the benign solvent to the poor solvent is 1: 0.8-1: 2.
10. The method for preparing multi-branched poly (glycolide-lactide) according to claim 9, wherein the poor solvent is selected from methanol, ethanol, n-hexane, n-heptane or diethyl ether.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851917A (en) * | 2021-01-28 | 2021-05-28 | 山东采采医疗科技有限公司 | Preparation method of polylactide caprolactone |
| CN112920384A (en) * | 2021-01-28 | 2021-06-08 | 山东谷雨春生物科技有限公司 | Preparation method of polyglycolide caprolactone |
| CN113429547A (en) * | 2021-06-30 | 2021-09-24 | 东南大学 | Preparation method of crystalline polylactic acid-glycolic acid |
| CN114940746A (en) * | 2022-06-17 | 2022-08-26 | 山东采采医疗科技有限公司 | Star-shaped lactide-glycolide copolymer and application thereof as drug sustained-release carrier |
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| CN1927906A (en) * | 2006-09-25 | 2007-03-14 | 南开大学 | Organism degradable star-type structure poly (glycolide-lactide) medicine carrier microsphere and preparation method thereof |
| CN101657487A (en) * | 2007-02-16 | 2010-02-24 | 阿克马法国公司 | Method for producing a copolymer of at least one cyclic monomer |
| US20170292109A1 (en) * | 2016-04-06 | 2017-10-12 | Sutapa Barua | Method of forming microparticles for use in cell seeding |
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2019
- 2019-12-27 CN CN201911376471.1A patent/CN111019107A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927906A (en) * | 2006-09-25 | 2007-03-14 | 南开大学 | Organism degradable star-type structure poly (glycolide-lactide) medicine carrier microsphere and preparation method thereof |
| CN101657487A (en) * | 2007-02-16 | 2010-02-24 | 阿克马法国公司 | Method for producing a copolymer of at least one cyclic monomer |
| US20170292109A1 (en) * | 2016-04-06 | 2017-10-12 | Sutapa Barua | Method of forming microparticles for use in cell seeding |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851917A (en) * | 2021-01-28 | 2021-05-28 | 山东采采医疗科技有限公司 | Preparation method of polylactide caprolactone |
| CN112920384A (en) * | 2021-01-28 | 2021-06-08 | 山东谷雨春生物科技有限公司 | Preparation method of polyglycolide caprolactone |
| CN113429547A (en) * | 2021-06-30 | 2021-09-24 | 东南大学 | Preparation method of crystalline polylactic acid-glycolic acid |
| CN113429547B (en) * | 2021-06-30 | 2022-03-08 | 东南大学 | Preparation method of crystalline polylactic acid-glycolic acid |
| CN114940746A (en) * | 2022-06-17 | 2022-08-26 | 山东采采医疗科技有限公司 | Star-shaped lactide-glycolide copolymer and application thereof as drug sustained-release carrier |
| CN114940746B (en) * | 2022-06-17 | 2024-04-26 | 山东采采医疗科技有限公司 | Star-shaped lactide-glycolide copolymer and its use as drug sustained-release carrier |
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