CN1583818A - Di(2-methoxyethoxy) aluminum sodium oxide catalytic synthesis of lactic acid-ethanediol copolymer - Google Patents
Di(2-methoxyethoxy) aluminum sodium oxide catalytic synthesis of lactic acid-ethanediol copolymer Download PDFInfo
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- CN1583818A CN1583818A CN 200410019626 CN200410019626A CN1583818A CN 1583818 A CN1583818 A CN 1583818A CN 200410019626 CN200410019626 CN 200410019626 CN 200410019626 A CN200410019626 A CN 200410019626A CN 1583818 A CN1583818 A CN 1583818A
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Abstract
Preparetion of biodegrading materials of poly-lactic acid - polyglycol-polylactic acid three block-copolymer for medical uses is achieved by: taking sodium bis(2-methoxyethoxy) aluminum hydride (Red-Al) for short: Red-Al as catalyst, copolymerizing for lactide (D,L -lactide, D,L - LA or L - lactide L- LA) and polyglycol (molecular weight 2000-20000), to synthesize high organisms and safety medical biodegradation materials. This process avoids using the current used octane acid stannous series catalysts, which are cell toxic. It makes polymerization controllable and can synthesize duoparental copolymers, which have specific molecular weight and different hydrophilicity according to the design required. The catalyst Red-Al is chemical pure reagent (70% methylbenzene solution, ACROS product) and nontoxic. The technology has no three wastes pollution, and high economically benefits.
Description
Technical field
The present invention relates to a kind of medical biodegradable material, particularly relate to polylactic acid-polyglycol-polylactic acid triblock copolymer class medical biodegradable material synthetic novel method.Use two (2-methoxyethoxy) sodium alanate (trade(brand)names: Red-Al, be called for short: Red-Al) carry out rac-Lactide (D for catalyzer, L-rac-Lactide or L-rac-Lactide) and polyoxyethylene glycol (PEG) be the copolymerization of starting raw material, belong to technical field of polymer chemistry.
Background technology
In recent years, along with medicine and biomedical science fast development worldwide, domestic and international demand sharp increase to medical biodegradable material.In the medical biodegradable material of various synthetic, the multipolymer that has hydrophobicity poly(lactic acid) block and a hydrophilic polyglycol block supports and there is important use aspect such as equivalent material thereby is paid attention to day by day in medicine controlled releasing, soft tissue repair, implantation sclerous tissues.At present both at home and abroad existing a more serious problem at this type of material aspect synthetic is: the commercial catalyst stannous octoate that is used for polyreaction has cytotoxicity, because can't be after the polyreaction with used stannous octoate catalyst by thoroughly removing in institute's synthetic polymer, this just gives this type of material as human pharmaceutical use, medical material, particularly longer-term Material Used (taking the carrier of medicine for a long time, the longer-term property implanted medical material etc.) brings insecurity hidden danger.Therefore, research and develop that novel nontoxic, high-efficiency polymerization catalysts is synthetic to have a task of top priority that height biological safety medical biodegradable material has become the focus that the scientists of being engaged in medical macromolecular materials research in the our times various countries pays close attention to and appealed to solve.Polymer institute of Nankai University and " absorption and separation function macromolecular material National Key Laboratory " Li Hong professor initiative under the Ministry of Science and Technology's great fundamental research early-stage Study special project (No.2002CCA02500) is subsidized adopt two (2-methoxyethoxy) sodium alanate catalyst to synthesize lactic acid-polyethylene glycol-lactic acid triblock copolymers medical biodegradable material and succeed.
Summary of the invention
The present invention utilizes two (2-methoxyethoxy) sodium alanate (trade(brand)names: Red-Al, be called for short: Red-Al) be catalyzer, cyclisation lactide dimer [D with lactic acid, the L-rac-Lactide (D, L-LA) or L-rac-Lactide (L-LA)] and polyoxyethylene glycol (PEG) be starting raw material through the medical degradation property polylactic acid-polyglycol-polylactic acid triblock copolymer of ring-opening copolymerization reaction synthesising biological.
Two (2-methoxyethoxy) sodium alanate catalyst molecule structures and chemical name and trade(brand)name are as follows:
Two (2-methoxyethoxy) sodium alanate
(Red-Al)
The beneficial effect of the biological polylactic acid-polyglycol-polylactic acid triblock copolymer of present method synthesis of medical is: it is non-toxic compound that this law is selected catalyzer for use, institute's synthetic biodegradable copolymer totally nontoxic.And can be according to the molecular weight and hydrophilic, the oleophylic performance thereof of rac-Lactide and polyoxyethylene glycol raw material feed ratio regulation and control institute synthetic copolymer.Institute's synthetic copolymer has the characteristics of narrow molecular weight distribution (PDI=1.10～1.20).Technology is simple, and the non-environmental-pollution thing generates.
Embodiment
With a certain amount of rac-Lactide (D, L-rac-Lactide or L-rac-Lactide) and polyoxyethylene glycol input reactor, vacuumize and fill with high pure nitrogen after removing air again, the nitrogen that outgases-fill operation triplicate press Red-Al and polyoxyethylene glycol then and is designed mol ratio with in the catalyzer Red-Al adding reactor.Remove under the vacuum and desolvate, then the off-response device.Reactor is under agitation slowly heated up under steady temperature (100～200 ℃) then, reaction certain hour (6～24 hours).Behind the stopped reaction, multipolymer is dissolved with methylene dichloride, then solute is precipitated out in anhydrous diethyl ether.Cross filtered product vacuum-drying at room temperature, dissolving-precipitation operation triplicate obtains faint yellow solid after the vacuum-drying, is institute's synthesising biological degradation property multipolymer.
Reaction formula is as follows:
M：D，L-LA；L-LA
With the tetrahydrofuran (THF) is solvent, and μ-Styragel packed column adopts the Waters-410 gel chromatograph to measure institute's synthetic copolymer molecular weight (be with the monodisperse polystyrene standard specimen and proofread and correct through pervasive value) under the room temperature.Institute's synthetic copolymer molecular weight and hydrophilic, oleophylic performance thereof can be according to rac-Lactide and the regulation and control of polyoxyethylene glycol raw material feed ratio, product molecular weight distribution narrow (1.10～1.20), and productive rate 〉=96%, product is faint yellow.
Embodiment 1
Pack in the reactor D of 14.4 grams, L-rac-Lactide and 30 gram molecular weights are 6000 polyoxyethylene glycol, and reactor is vacuumized, and use nitrogen replacement then, the nitrogen that outgases-fill operation triplicate.By polyoxyethylene glycol: catalyzer=50: 1 (mol ratio) adds 1 milliliter of Red-Al toluene solution, and (concentration is 1.0 * 10
-1Mol), remove under the vacuum and desolvate, then the off-response still.Reactor is slowly heated, reacted 12 hours down for 120 ℃ in steady temperature.Behind the stopped reaction, reactor is chilled to room temperature, adds methylene dichloride dissolution kettle interpolymer then.Then solution slowly is poured in the excessive anhydrous diethyl ether polymer precipitation is come out.Filter, precipitation is placed vacuum drying oven, 40 ℃ of vacuum-dryings 24 hours, dissolving-precipitation operation triplicate obtained pale yellow powder shape solid after the vacuum-drying.Productive rate 97%, molecular weight of copolymer are 8.3～8.6 * 10
3, PDI≤1.20.
Claims (3)
1. the method for two (2-methoxyethoxy) sodium alanate synthesis of medical polylactic acid-polyglycol-copolymer of poly lactic acid, it is characterized in that: adopting two (2-methoxyethoxy) sodium alanates is catalyzer, rac-Lactide and polyoxyethylene glycol are that starting raw material carries out bulk copolymerization and closes reaction, and reaction formula is as follows:
M：D，L-LA；L-LA
2. the method for two (2-methoxyethoxy) sodium alanate synthesis of medical polylactic acid-polyglycol-copolymer of poly lactic acid according to claim 1, it is characterized in that: rac-Lactide is D, L-rac-Lactide or L-rac-Lactide.
3. the method for two (2-methoxyethoxy) sodium alanate synthesis of medical polylactic acid-polyglycol-copolymer of poly lactic acid according to claim 1, it is characterized in that: molecular weight polyethylene glycol is 2000-20000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410019626 CN1235934C (en) | 2004-06-15 | 2004-06-15 | Di(2-methoxyethoxy) aluminum sodium oxide catalytic synthesis of lactic acid-ethanediol copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410019626 CN1235934C (en) | 2004-06-15 | 2004-06-15 | Di(2-methoxyethoxy) aluminum sodium oxide catalytic synthesis of lactic acid-ethanediol copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1583818A true CN1583818A (en) | 2005-02-23 |
| CN1235934C CN1235934C (en) | 2006-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410019626 Expired - Fee Related CN1235934C (en) | 2004-06-15 | 2004-06-15 | Di(2-methoxyethoxy) aluminum sodium oxide catalytic synthesis of lactic acid-ethanediol copolymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864062A (en) * | 2010-06-07 | 2010-10-20 | 中国科学院宁波材料技术与工程研究所 | Unsaturated polylactic acid block copolymer and preparation method thereof |
-
2004
- 2004-06-15 CN CN 200410019626 patent/CN1235934C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864062A (en) * | 2010-06-07 | 2010-10-20 | 中国科学院宁波材料技术与工程研究所 | Unsaturated polylactic acid block copolymer and preparation method thereof |
| CN101864062B (en) * | 2010-06-07 | 2012-05-23 | 中国科学院宁波材料技术与工程研究所 | Unsaturated polylactic acid block copolymer and preparation method thereof |
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| Publication number | Publication date |
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| CN1235934C (en) | 2006-01-11 |
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