CN101445595B - Poly glycolide lactide (PGLA), preparation method and application thereof - Google Patents
Poly glycolide lactide (PGLA), preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a poly glycolide lactide (PGLA), a preparation method and the application thereof. The preparation method is characterized by comprising the steps: glycolide and lactide are heated to be melted; then, under the condition of decompression and the existence of catalytic amounts of catalyst, copolymerization is carried out on the glycolide and the lactide in inert atmosphere, and the catalyst comprises the mixture of metallic tin salt, alkyl magnesium and taurine, wherein, the mol ratio of the metallic tin salt, the alkyl magnesium and the taurine is 1:0.1-1:0.1-0.5. The PGLA prepared by the method has the molecular weight of 0.08-0.3 million, and can be used for preparing surgical suture. The method needs less reaction time and high productive rate, and solves the problem that polymer is difficult to take out after reaction; meanwhile, the PGLA is easier to package and carry after grain-sized dicing, and is not added with any solvent, so as not to cause environmental pollution.
Description
Technical field
The present invention relates to poly (glycolide-lactide) and its production and application.
Background technology
Poly (glycolide-lactide) (PLGA) is nontoxic Biodegradable polymer, and this polymkeric substance is good biocompatibility in vivo, and degraded product lactic acid and oxyacetic acid can participate in the metabolism of human body, finally forms carbonic acid gas and water is excreted.Be widely used in biomedicine fields such as operating sutures, fracture fixation, medicament slow release, organizational project.
At present, poly (glycolide-lactide) (PLGA) synthetic has two kinds of approach, and a kind of is to be the raw material direct condensation with lactic acid, oxyacetic acid, and the PLGA molecular weight that this method obtains is lower, and application is very restricted; Another kind is earlier with lactic acid and oxyacetic acid difference synthesising biological degradable material poly(lactic acid) intermediate---rac-Lactide and glycollide, again rac-Lactide and glycollide are carried out copolyreaction and obtain PLGA, the PLGA molecular weight height that this method obtains can satisfy the requirement of strength of medical field product such as nail etc. fully.
At present, the disclosed relevant poly (glycolide-lactide) preparation method's of Chinese patent patent is mainly as follows:
Chinese patent (patent No. 200480002454.7) is a catalyzer with the trifluoromethayl sulfonic acid ester, and adds polymeric additive, under-20～150 ℃ of temperature, the reaction times in 48 hours, by solution polymerization poly (glycolide-lactide).
Chinese patent (patent No. 200710030498.6) uses the catalyzer that comprises Primary Catalysts, initiator, coinitiator three components; temperature of reaction is at 100～200 ℃; monomer/catalyst (mol ratio) is 20000～500000; under protection of inert gas or vacuum, reacted 1～200 hour, copolymerization poly (glycolide-lactide).
Chinese patent (patent No. 200410025458.9) employing supercritical carbon dioxide fluid is a reaction medium, with metal, metal oxide or metal-salt is initiator, initiator amount is 0.01～1wt% of raw material consumption, temperature of reaction is 50～90 ℃, reaction times 10～70h, polymerization has obtained poly (glycolide-lactide).
As everyone knows, poly (glycolide-lactide) is because the viscosity height, in container, be difficult under the normal temperature take out, when carrying out pilot scale or big reactor reaction, though at high temperature be in molten state, but high temperature takes out all difficulty or ease operations of material and following operation moulding down, and the above patent reaction times is all longer, is not suitable for suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of poly (glycolide-lactide) and its production and application, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
With glycollide and rac-Lactide heating and melting, in the presence of the catalyzer of decompression and catalytic amount, carry out copolymerization in the inert atmosphere then, temperature of reaction is 100～160 ℃, and the reaction times is 8～15 hours, preferred 10～12h, collect poly (glycolide-lactide) then from reaction product, molecular weight is 8～300,000;
Pressure during reaction is-0.01～0.1Mpa;
The weight ratio of glycollide and rac-Lactide is: glycollide: rac-Lactide=1: 0.5～6;
Described catalyzer is the mixture of metal pink salt, alkane base Magnesium and taurine, and the mol ratio of metal pink salt, alkane base Magnesium and taurine is: 1: 0.1～1: 0.1～0.5;
Preferably, the catalyst weight consumption is 0.01～0.1wt% of monomer consumption;
Described metal pink salt is selected from a kind of in stannous octoate or the tin protochloride;
The general structure of described Wan Ji Magnesium is as follows:
R
1-Mg-R
2, R wherein
1, R
2Be respectively the alkyl of C atomicity between 2～10, preferred Wan Ji Magnesium is Er Yi Ji Magnesium or Er Ding Ji Magnesium;
Described taurine can adopt the commercially available prod, is 99.5% product as one-tenth chemical industry company limited of Shanghai nation specification;
Preferably, with glycollide and rac-Lactide heating and melting, and reach 2～3 relative viscosities after carry out copolyreaction;
Preferably, the copolymerization of glycollide and rac-Lactide is carried out in the bottom is provided with the reactor of aperture, and described aperture is provided with valve, after reaction finishes, feeds rare gas element such as N
2, poly (glycolide-lactide) is extruded from the aperture of reactor bottom, after the poly (glycolide-lactide) cooling of extrusion, carry out pelletizing, obtain the poly (glycolide-lactide) pellet.
The poly (glycolide-lactide) that method of the present invention obtains, molecular weight is 8～300,000, can be used for preparing suture.
Method of the present invention, the reaction times is few, and the productive rate height has not only solved reaction and has finished the shortcoming that the post polymerization thing is difficult to take out, and is easier to packing after the pelletizing simultaneously, carries, and does not add solvent, environmentally safe.
Embodiment:
Embodiment 1
Glycollide and rac-Lactide are placed in the vacuum drying oven, 55 ℃ of temperature, pressure is-0.05MPa to take out after dry 3.5 hours;
Take by weighing above-mentioned glycollide 300g and rac-Lactide 900g respectively and add reactor, logical N
2Eliminated the air in the reactor in about 10 minutes; add composite catalyst stannous octoate 0.36g, Er Yi Ji Magnesium 0.18g and taurine 0.072g; close the turnover valve; the 0.1MPa that reduces pressure, heating is also opened and is stirred, after lactide dissolves fully and reaches 2.4827 relative viscosities; stop to stir; stirring rake is extracted charge level, and the control material is warm at 100 ℃ simultaneously, isothermal reaction 10 hours.After reaction finished, Open valve returned to normal pressure with reacting kettle inner pressure, and opened reactor bottom ports valve, logical N
2Material is extruded from the aperture of reactor bottom, go into the dicing machine pelletizing, obtain the poly (glycolide-lactide) pellet by tank cooling rear haulage.The poly (glycolide-lactide) Mn=126437 of gained, Mw/Mn=1.637.
Embodiment 2
Glycollide and rac-Lactide are placed in the vacuum drying oven, 50 ℃ of temperature, pressure is-0.06MPa to take out after dry 3.5 hours;
Take by weighing above-mentioned glycollide 400g and rac-Lactide 700g respectively and add reactor, logical N
2Eliminated the air in the reactor in about 15 minutes; add composite catalyst stannous octoate 0.44g, Er Yi Ji Magnesium 0.176g and taurine 0.144g; close the turnover valve; the 0.1MPa that reduces pressure, heating is also opened and is stirred, after lactide dissolves fully and reaches 2.3096 relative viscosities; stop to stir; stirring rake is extracted charge level, and the control material is warm at 110 ℃ simultaneously, isothermal reaction 12 hours.After reaction finished, Open valve returned to normal pressure with reacting kettle inner pressure, and opened reactor bottom ports valve, logical N
2Material is extruded from the aperture of reactor bottom, go into the dicing machine pelletizing, obtain the poly (glycolide-lactide) pellet by tank cooling rear haulage.The poly (glycolide-lactide) Mn=203851 of gained, Mw/Mn=1.824.
Embodiment 3
Glycollide and rac-Lactide are placed in the vacuum drying oven, 55 ℃ of temperature, pressure is-0.01MPa to take out after dry 4 hours;
Take by weighing above-mentioned glycollide 200g and rac-Lactide 1100g respectively and add reactor, logical N
2Eliminated the air in the reactor in about 15 minutes; add composite catalyst stannous octoate 0.65g, Er Ding Ji Magnesium 0.2925g and taurine 0.26g; close the turnover valve; the 0.1MPa that reduces pressure, heating is also opened and is stirred, after lactide dissolves fully and reaches 2.8275 relative viscosities; stop to stir; stirring rake is extracted charge level, and the control material is warm at 120 ℃ simultaneously, isothermal reaction 15 hours.After reaction finished, Open valve returned to normal pressure with reacting kettle inner pressure, and opened reactor bottom ports valve, logical N
2Material is extruded from the aperture of reactor bottom, go into the dicing machine pelletizing, obtain the poly (glycolide-lactide) pellet by tank cooling rear haulage.The poly (glycolide-lactide) Mn=234308 of gained, Mw/Mn=1.871.
Embodiment 4
Glycollide and rac-Lactide are placed in the vacuum drying oven, 58 ℃ of temperature, pressure is-0.1MPa to take out after dry 4 hours;
Take by weighing above-mentioned glycollide 200g and rac-Lactide 800g respectively and add reactor, logical N
2Eliminated the air in the reactor in about 20 minutes; add composite catalyst stannous octoate 0.45g, Er Ding Ji Magnesium 0.144g and taurine 0.1575g; close the turnover valve; the 0.1MPa that reduces pressure, heating is also opened and is stirred, after lactide dissolves fully and reaches 2.7327 relative viscosities; stop to stir; stirring rake is extracted charge level, and the control material is warm at 130 ℃ simultaneously, isothermal reaction 15 hours.After reaction finished, Open valve returned to normal pressure with reacting kettle inner pressure, and opened reactor bottom ports valve, logical N
2Material is extruded from the aperture of reactor bottom, go into the dicing machine pelletizing, obtain the poly (glycolide-lactide) pellet by tank cooling rear haulage.The poly (glycolide-lactide) Mn=281952 of gained, Mw/Mn=1.958.
Embodiment 5
Glycollide and rac-Lactide are placed in the vacuum drying oven, 53 ℃ of temperature, pressure is-0.1MPa to take out after dry 4 hours;
Take by weighing above-mentioned glycollide 500g and rac-Lactide 500g respectively and add reactor, logical N
2Eliminated the air in the reactor in about 15 minutes; add composite catalyst tin protochloride 0.8g, Er Yi Ji Magnesium 0.48g and taurine 0.28g; close the turnover valve; the 0.1MPa that reduces pressure, heating is also opened and is stirred, after lactide dissolves fully and reaches 2.2965 relative viscosities; stop to stir; stirring rake is extracted charge level, and the control material is warm at 140 ℃ simultaneously, isothermal reaction 13 hours.After reaction finished, Open valve returned to normal pressure with reacting kettle inner pressure, and opened reactor bottom ports valve, logical N
2Material is extruded from the aperture of reactor bottom, go into the dicing machine pelletizing, obtain the poly (glycolide-lactide) pellet by tank cooling rear haulage.The poly (glycolide-lactide) Mn=173818 of gained, Mw/Mn=1.563.
Embodiment 6
Glycollide and rac-Lactide are placed in the vacuum drying oven, 56 ℃ of temperature, pressure is-0.1MPa to take out after dry 3.5 hours;
Take by weighing above-mentioned glycollide 700g and rac-Lactide 400g respectively and add reactor, logical N
2Eliminated the air in the reactor in about 15 minutes; add composite catalyst tin protochloride 0.715g, Er Ding Ji Magnesium 0.5005g and taurine 0.3218g; close the turnover valve; the 0.1MPa that reduces pressure, heating is also opened and is stirred, after lactide dissolves fully and reaches 2.6381 relative viscosities; stop to stir; stirring rake is extracted charge level, and the control material is warm at 130 ℃ simultaneously, isothermal reaction 11 hours.After reaction finished, Open valve returned to normal pressure with reacting kettle inner pressure, and opened reactor bottom ports valve, logical N
2Material is extruded from the aperture of reactor bottom, go into the dicing machine pelletizing, obtain the poly (glycolide-lactide) pellet by tank cooling rear haulage.The poly (glycolide-lactide) Mn=102846 of gained, Mw/Mn=1.5932.
Claims (10)
1. the preparation method of poly (glycolide-lactide), it is characterized in that, comprise the steps: glycollide and rac-Lactide heating and melting, then in the presence of the catalyzer of decompression and catalytic amount, carry out copolymerization in the inert atmosphere, described catalyzer is the mixture of metal pink salt, alkyl magnesium and taurine, and the mol ratio of metal pink salt, alkyl magnesium and taurine is: 1: 0.1～1: 0.1～0.5;
2. method according to claim 1 is characterized in that, temperature of reaction is 100～160 ℃, and the reaction times is 8～15 hours, and the pressure during reaction is-0.01～0.1MPa.
3. method according to claim 1 is characterized in that, the catalyst weight consumption is 0.01～0.1wt% of monomer consumption.
4. method according to claim 1 is characterized in that, described metal pink salt is selected from a kind of in stannous octoate or the tin protochloride.
5. method according to claim 1 is characterized in that, the general structure of described alkyl magnesium is as follows:
R
1-Mg-R
2, R wherein
1, R
2Be respectively the alkyl of C atomicity between 2～10.
6. method according to claim 5 is characterized in that, alkyl magnesium is magnesium ethide or dibutylmagnesium.
7. method according to claim 1 is characterized in that, with glycollide and rac-Lactide heating and melting, and reach 2～3 relative viscosity after carry out copolyreaction.
8. method according to claim 1, it is characterized in that, the copolymerization of glycollide and rac-Lactide is carried out in the bottom is provided with the reactor of aperture, described aperture is provided with valve, after reaction finishes, feeds rare gas element, poly (glycolide-lactide) is extruded from the aperture of reactor bottom, after the poly (glycolide-lactide) cooling that extrudes, carry out pelletizing, obtain the poly (glycolide-lactide) pellet.
9. adopt the poly (glycolide-lactide) of each described method preparation of claim 1～8, molecular weight is 8～300,000.
10. the application of poly (glycolide-lactide) according to claim 9 is characterized in that, is used to prepare suture.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107059158A (en) * | 2017-05-19 | 2017-08-18 | 中国纺织科学研究院 | Poly (glycolide-lactide) and polycaprolactone composite fibre, its preparation method, purposes and operation suture thread |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988291A (en) * | 2019-03-28 | 2019-07-09 | 杭州华惟生物医药有限公司 | Poly (glycolide-co-lactide) copolymer ultrasonic synthetic method |
| CN111926408A (en) * | 2020-07-06 | 2020-11-13 | 中国纺织科学研究院有限公司 | Purple poly (glycolide-lactide) fiber, preparation method and application thereof and surgical suture |
| CN112920384B (en) * | 2021-01-28 | 2023-03-21 | 山东谷雨春生物科技有限公司 | Preparation method of polyglycolide caprolactone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107059158A (en) * | 2017-05-19 | 2017-08-18 | 中国纺织科学研究院 | Poly (glycolide-lactide) and polycaprolactone composite fibre, its preparation method, purposes and operation suture thread |
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