CN115806539A - Method for preparing 3-methyl glycolide - Google Patents
Method for preparing 3-methyl glycolide Download PDFInfo
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- CN115806539A CN115806539A CN202211674228.XA CN202211674228A CN115806539A CN 115806539 A CN115806539 A CN 115806539A CN 202211674228 A CN202211674228 A CN 202211674228A CN 115806539 A CN115806539 A CN 115806539A
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- glycolide
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- 238000000034 method Methods 0.000 title claims abstract description 18
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims abstract description 35
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005336 cracking Methods 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 9
- 238000002425 crystallisation Methods 0.000 abstract description 8
- 230000008025 crystallization Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000012648 alternating copolymerization Methods 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000012974 tin catalyst Substances 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 238000003918 potentiometric titration Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- PJRSUKFWFKUDTH-JWDJOUOUSA-N (2s)-6-amino-2-[[2-[[(2s)-2-[[(2s,3s)-2-[[(2s)-2-[[2-[[(2s)-2-[[(2s)-6-amino-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[(2-aminoacetyl)amino]-4-methylsulfanylbutanoyl]amino]propanoyl]amino]-3-hydroxypropanoyl]amino]hexanoyl]amino]propanoyl]amino]acetyl]amino]propanoyl Chemical compound CSCC[C@H](NC(=O)CN)C(=O)N[C@@H](C)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C)C(=O)NCC(=O)N[C@@H](C)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](C)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(N)=O PJRSUKFWFKUDTH-JWDJOUOUSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- -1 cyclic ester Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 108010021753 peptide-Gly-Leu-amide Proteins 0.000 description 1
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Abstract
The invention discloses a preparation method of 3-methyl glycolide, which comprises the steps of adding lactide, glycolide, tin catalysts and initiators into a reaction kettle, then continuously adding the rest glycolide in a molten liquid form or adding the rest glycolide in batches, forming alternating copolymerization oligomers as much as possible, then cracking, and collecting lactide mixtures. Then the mixed lactide is separated and purified respectively by a method of repeated gradient melt crystallization. 3-methyl glycolide is obtained. The novel preparation method of the 3-methyl glycolide avoids the use of organic solvents, utilizes an industrial conventional method for preparing lactide, develops a valuable degradable material monomer 3-methyl glycolide through a method for preparing alternating glycolide oligomer cracking, and can be prepared in a large scale; the reaction path of the invention is easy for industrial mass production, and has the characteristics of low cost, safety, environmental protection and the like.
Description
Technical Field
The invention relates to a method for preparing asymmetric cyclic ester, in particular to an economical method for preparing 3-methyl glycolide capable of being produced in large scale, belonging to the technical field of synthesis of high polymer materials.
Background
With the continuous development of polymer chemistry and the continuous enhancement of environmental awareness of people, degradable polymer materials receive more and more attention. The existing degradable high polymer materials are rare, the prepared raw material monomers are more variable, and if new degradable material monomers can be additionally prepared, the degradable materials can be greatly enriched to replace more slowly degraded petrochemical materials, so that the significance is great.
The PGLA910 surgical suture which is most famous and promoted by Hengsheng company is prepared by a preparation method of ring-opening uniform random copolymerization of glycolide and lactide, is influenced by steric hindrance, and the ring-opening polymerization activity of catalyzing glycolide is usually much higher than that of catalyzing lactide, so that the preparation of a uniform copolymer of glycolide and lactide is very difficult. Although the method of supplementing the high-activity monomer can be adopted for improvement in the polymerization process, the reaction has the advantages of higher polymerization speed, high viscosity rise speed and even crystallization precipitation, and the problem of heavy difficulty in uniformly mixing the supplemented monomer is solved. A preferred method of preparation is to use an asymmetric monomer, 3-methylglycolide, for ring opening polymerization to allow easy preparation of homogeneous copolymers, even alternating copolymers. And the ring-opening reaction activity of the 3-methyl glycolide is very similar to that of glycolide, so that the process for preparing PGLA910 is greatly simplified.
At present, no report of scale product production is found in the preparation of 3-methyl glycolide, the research is limited to the preparation of a small amount of laboratory basic research, the reported preparation method is also limited to a small molecule cyclization method, for example, the preparation method is prepared by cyclization by a small molecule benzene ring removal method as reported in patent documents 1 and 2, and the preparation method is prepared by cyclization by a small molecule hydrogen halide removal method as reported in patent documents 3 and 4. These methods are not suitable for mass production due to the complexity of small molecules, the need of using a large amount of solvent, and the high cost of multi-step reaction, separation and purification.
Disclosure of Invention
The invention aims to find a preparation path which is easy for process large-scale production for valuable degradable material monomer 3-methyl glycolide and expand the variety of degradable materials. Meanwhile, the invention also aims to facilitate the preparation of the homogeneous copolymer PGLA or PLGA by obtaining the 3-methyl glycolide, in particular to prepare the homogeneous copolymer PGLA910 surgical suture and simplify the process.
The invention discloses a preparation method of 3-methyl glycolide, which adopts the following technical scheme:
1. uniformly mixing glycolide and lactide according to a mass ratio of (4;
wherein the alternating glycolide-lactide copolymer adopts a mode of continuously adding high-activity monomer glycolide or adding glycolide in batches to control the arrangement of the glycolide-lactide on a molecular chain;
2. adding a stannous chloride or stannous octoate catalyst in an amount of 0.01-0.7% of the mass of the total lactide monomer, adding glycolic acid or lactic acid as an initiator in an amount of 4-0.1% of the mass of the total lactide monomer, sealing, vacuumizing, introducing nitrogen, heating to 100 ℃, melting, and uniformly mixing;
3. continuously adding liquid glycolide, wherein the continuous glycolide adding amount is 20-40% of the total lactide monomer mass, converting into a cracking mode when the molecular weight reaches 2000-10000, and heating to 200-300 ℃ for cracking, preferably 220-280 ℃, and most preferably 230-260 ℃; distilling under reduced pressure to collect the mixture; in the cracking link, a path is adopted for melting and continuously feeding, namely, the cracked oligomer is slowly melted and is injected into a cracking kettle, and the mixed lactide is collected by reduced pressure distillation at the other end;
4. and collecting the obtained mixture, and repeatedly melting, crystallizing, eluting, purifying and separating to obtain the 3-methyl glycolide.
Recrystallizing the lactide in the step 1) twice by anhydrous ethyl acetate;
recrystallizing the glycolide obtained in the step 1) twice by using anhydrous ethyl acetate;
the preferred mixing ratio of glycolide and lactide in step 1) of the present invention is: the preferable mass ratio is as follows: (7): (5;
the catalyst stannous chloride or stannous octoate added in the step 2) of the invention has the addition amount based on the mass of the total lactide monomer: 0.01wt% -0.7 wt%;
the initiator added in step 2) of the present invention is selected from: glycolic acid or lactic acid; the preferred ratio is based on the total lactide monomer mass: 4wt% -0.1 wt%.
The invention has the positive effects that: provides a new preparation method of 3-methyl glycolide, avoids the use of organic solvent, develops valuable degradable material monomer 3-methyl glycolide by a method for preparing lactide-ethylene-propylene-lactide oligomer cracking, and can be prepared in a large scale; the reaction path of the invention is easy for industrial mass production, and has the characteristics of low cost, safety, environmental protection and the like; overcomes the defects that the traditional preparation method of the 3-methyl glycolide is not beneficial to mass production due to the complexity of small molecules, the use of a large amount of solvents, multi-step reaction, higher cost of separation and purification and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 3-methyl glycolide according to the invention;
FIG. 2 is a mass spectrum of 3-methyl glycolide according to the invention.
Detailed Description
The present invention is further illustrated by the following examples, which do not limit the present invention in any way, and any modifications or changes that can be easily made by a person skilled in the art to the present invention will fall within the scope of the claims of the present invention without departing from the technical solution of the present invention.
Example 1
Putting 144 g of purified and dried lactide (recrystallized twice by anhydrous ethyl acetate) and 12g of glycolide (recrystallized twice by anhydrous ethyl acetate) into a reaction kettle, adding 0.1g of stannous chloride catalyst and 1.5g of initiator glycolic acid, sealing, vacuumizing, introducing nitrogen, heating to 100 ℃, melting, uniformly mixing, continuously adding 104 g of liquid glycolide, monitoring the change of molecular weight by means of sampling potentiometric titration, converting into a cracking mode when the molecular weight reaches about 7000, heating to 230-250 ℃ for cracking, and distilling under reduced pressure to collect a mixture; and putting the collected mixture into a melting crystallization reaction device, and repeatedly melting, crystallizing, eluting, purifying and separating to obtain the 3-methyl glycolide with a lower melting point, wherein the nuclear magnetic hydrogen spectrogram and the mass spectrogram of the 3-methyl glycolide are shown in figures 1 and 2.
Example 2
Putting 144 g of purified and dried lactide (recrystallized twice by anhydrous ethyl acetate) and 11.6 g of glycolide (recrystallized twice by anhydrous ethyl acetate), adding a small amount of 0.12g of stannous chloride catalyst and 1.2g of glycolic acid initiator, sealing, vacuumizing, introducing nitrogen, heating to 105 ℃, melting, uniformly mixing, dividing 104 g of molten liquid glycolide into four batches, adding one batch (about 26 g) every 5 minutes, monitoring the change of the molecular weight by a sampling potentiometric titration mode after the glycolide is added, converting into a cracking mode when the molecular weight reaches about 9000, heating to 230-250 ℃ for cracking, and distilling under reduced pressure to collect a mixture; collecting the obtained mixture, placing into a melt crystallization reaction device, repeatedly melting, crystallizing, eluting, purifying and separating to obtain 3-methyl glycolide product with melting point of 70-71 deg.C, wherein the nuclear magnetic hydrogen spectrogram and mass spectrogram of 3-methyl glycolide are shown in figure 1 and figure 2.
Example 3
Putting 144 g of purified and dried lactide (recrystallized twice by anhydrous ethyl acetate) and 58 g of glycolide (recrystallized twice by anhydrous ethyl acetate) into a reaction kettle, adding a small amount of 0.08g of stannous chloride catalyst and 2g of glycolic acid initiator, sealing, vacuumizing, introducing nitrogen, heating to 100 ℃, melting, uniformly mixing, dividing 58 g of molten glycolide into two batches, adding one batch (about 29 g) every 5 minutes, monitoring the change of molecular weight by a sampling potentiometric titration mode after the glycolide is added, converting into a cracking mode when the molecular weight reaches about 5000, heating to 230-250 ℃ for cracking, and distilling under reduced pressure to collect a mixture; and putting the collected mixture into a melt crystallization reaction device, and repeatedly melting, crystallizing, eluting, purifying and separating to obtain a 3-methyl glycolide product with the melting point of 70-71 ℃, wherein the nuclear magnetic hydrogen spectrogram and the mass spectrogram of the 3-methyl glycolide are shown in figures 1 and 2.
Example 4
Putting 144 g of purified and dried lactide (recrystallized twice by anhydrous ethyl acetate) and 96 g of glycolide (recrystallized twice by anhydrous ethyl acetate) into a reaction kettle, adding a small amount of 0.5g of stannous octoate catalyst and 3g of diethylene glycol initiator, sealing, vacuumizing, introducing nitrogen, heating to 105 ℃, melting, uniformly mixing, after 5 minutes, adding 20 g of residual molten liquid glycolide at one time, monitoring the change of molecular weight by a sampling potentiometric titration mode after the glycolide is added, converting into a cracking mode when the molecular weight reaches about 4000, heating to 230-250 ℃, cracking, and distilling under reduced pressure to collect a mixture; collecting the obtained mixture, placing into a melt crystallization reaction device, repeatedly melting, crystallizing, eluting, purifying and separating to obtain 3-methyl glycolide product with melting point of 70-71 deg.C, and its nuclear magnetic hydrogen spectrum and mass spectrum are shown in FIG. 1 and FIG. 2.
Example 5
Putting 144 g of purified and dried lactide (recrystallized twice by anhydrous ethyl acetate) and 116 g of glycolide (recrystallized twice by anhydrous ethyl acetate) into a reaction kettle, adding a small amount of 0.4g of stannous octoate catalyst and 3.5g of diethylene glycol, sealing, vacuumizing, introducing nitrogen, heating to 105 ℃, melting, uniformly mixing, monitoring the change of molecular weight by means of sampling potentiometric titration, converting into a cracking mode when the molecular weight reaches about 3000, heating to 230-250 ℃, cracking, distilling under reduced pressure and collecting a mixture; and putting the collected mixture into a melt crystallization reaction device, and repeatedly melting, crystallizing, eluting, purifying and separating to obtain a 3-methyl glycolide product with the melting point of 70-71 ℃, wherein the nuclear magnetic hydrogen spectrogram and the mass spectrogram of the 3-methyl glycolide are shown in figures 1 and 2.
Example 6
144 g of lactide (recrystallized twice from anhydrous ethyl acetate) and 96 g of glycolide (recrystallized twice from anhydrous ethyl acetate) which are purified and dried are taken and put into a reaction kettle, and a small amount of 0.6g of stannous octoate catalyst and 4g of diethylene glycol are added
Sealing and vacuumizing an initiator, introducing nitrogen, heating to 105 ℃, melting, uniformly mixing, monitoring the change of the molecular weight by a sampling potentiometric titration mode after 5 minutes, converting into a cracking mode when the molecular weight reaches about 3000, heating to 230-250 ℃, cracking, and distilling under reduced pressure to collect a mixture. And putting the collected mixture into a melt crystallization reaction device, and repeatedly melting, crystallizing, eluting, purifying and separating to obtain a 3-methyl glycolide product with the melting point of 70-71 ℃, wherein the nuclear magnetic hydrogen spectrogram and the mass spectrogram of the 3-methyl glycolide are shown in figures 1 and 2.
The 3-methyl glycolide monomer prepared by the invention has great significance in the preparation of degradable materials, and the provided reaction path is easy for industrial large-scale production and has the characteristics of low cost, safety, environmental protection and the like. Will be an important component of the degradable material.
Claims (4)
1. A preparation method of 3-methyl glycolide comprises the following steps:
1) Glycolide and lactide were mixed at a mass ratio (4: 1 to 2: 3) Mixing uniformly;
wherein the alternating glycolide-lactide copolymer adopts a mode of continuously adding high-activity monomer glycolide or adding glycolide in batches to control the arrangement of the glycolide-lactide on a molecular chain;
2) Adding a stannous chloride or stannous octoate catalyst in an amount of 0.01-0.7% of the mass of the total lactide monomer, adding glycolic acid or lactic acid as an initiator in an amount of 4-0.1% of the mass of the total lactide monomer, sealing, vacuumizing, introducing nitrogen, heating to 100 ℃, melting, and uniformly mixing;
3) Continuously adding liquid glycolide, wherein the mass of the continuously added glycolide is 20-40% of the mass of the total lactide monomer, converting into a cracking mode when the molecular weight reaches 2000-10000, and heating to 200-300 ℃ for cracking; distilling under reduced pressure to collect the mixture; in the cracking link, a path is adopted for melting and continuous feeding, namely, the cracking oligomer is slowly melted and is injected into a cracking kettle, and the mixed lactide is collected by reduced pressure distillation at the other end;
4) And collecting the obtained mixture, and repeatedly melting, crystallizing, eluting, purifying and separating to obtain the 3-methyl glycolide.
2. The process for producing 3-methylglycolide according to claim 1, wherein:
recrystallizing the lactide obtained in the step 1) twice through anhydrous ethyl acetate;
the glycolide was recrystallized twice from anhydrous ethyl acetate.
3. The process for producing 3-methylglycolide according to claim 1, wherein: the preferable mass mixing ratio of the glycolide and the lactide in the step 1) is as follows: (7; more preferred ratios are: (5.
4. The process for producing 3-methylglycolide according to claim 1, wherein:
the cracking temperature in step 3) is preferably 220-280 ℃, more preferably 230-260 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960152A (en) * | 1974-01-21 | 1976-06-01 | American Cyanamid Company | Surgical sutures of unsymmetrically substituted 1,4-dioxane-2,5-diones |
| CN107602834A (en) * | 2017-09-29 | 2018-01-19 | 天津理工大学 | The preparation method of lactide glycolide block copolymer |
| CN108546328A (en) * | 2018-05-11 | 2018-09-18 | 中国科学院长春应用化学研究所 | The guiding assemble method and block copolymer template of a kind of block copolymer, manufacturing cycle nanostructure |
| CN110283305A (en) * | 2019-06-12 | 2019-09-27 | 山东谷雨春生物科技有限公司 | A kind of preparation method of pharmaceutical Biodegradable polymer material poly (glycolide-lactide) |
| CN110563695A (en) * | 2019-09-22 | 2019-12-13 | 苏州格里克莱新材料有限公司 | Preparation method of mixture of glycolide and lactide |
| CN113717362A (en) * | 2021-04-30 | 2021-11-30 | 南京威尔药业科技有限公司 | Suspension polymerization preparation method of injectable lactide-glycolide copolymer |
| CN115386070A (en) * | 2022-08-03 | 2022-11-25 | 山东谷雨春生物科技有限公司 | Production process of medicinal polymer auxiliary material poly (glycolide-lactide) |
-
2022
- 2022-12-26 CN CN202211674228.XA patent/CN115806539A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960152A (en) * | 1974-01-21 | 1976-06-01 | American Cyanamid Company | Surgical sutures of unsymmetrically substituted 1,4-dioxane-2,5-diones |
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| CN110563695A (en) * | 2019-09-22 | 2019-12-13 | 苏州格里克莱新材料有限公司 | Preparation method of mixture of glycolide and lactide |
| CN113717362A (en) * | 2021-04-30 | 2021-11-30 | 南京威尔药业科技有限公司 | Suspension polymerization preparation method of injectable lactide-glycolide copolymer |
| CN115386070A (en) * | 2022-08-03 | 2022-11-25 | 山东谷雨春生物科技有限公司 | Production process of medicinal polymer auxiliary material poly (glycolide-lactide) |
Non-Patent Citations (2)
| Title |
|---|
| VLADIMIR BOTVIN等: "Intermolecular "zipper" type depolymerization of oligomeric molecules of lactic and glycolic acids prepacked as paired associates", POLYMER DEGRADATION AND STABILITY, vol. 146, pages 126 - 131, XP085304123, DOI: 10.1016/j.polymdegradstab.2017.10.004 * |
| VLADIMIR BOTVIN等: "Kinetic Study of Depolymerization of Lactic and Glycolic Acid Oligomers in the Presence of Oxide Catalysts", POLYMERS, vol. 12, pages 2395 * |
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