CN1238399C - Technology method of synthesizing medical biodegradable material foom di(2-methoxy ethoxy) aluminium sodium hydride - Google Patents
Technology method of synthesizing medical biodegradable material foom di(2-methoxy ethoxy) aluminium sodium hydride Download PDFInfo
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- CN1238399C CN1238399C CN 200410018604 CN200410018604A CN1238399C CN 1238399 C CN1238399 C CN 1238399C CN 200410018604 CN200410018604 CN 200410018604 CN 200410018604 A CN200410018604 A CN 200410018604A CN 1238399 C CN1238399 C CN 1238399C
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Abstract
The present invention relates to a medical biodegradable material, which particularly relates to a new technological method of the synthesis of polyester resin materials. The present invention is characterized in that sodium bis(2-methoxyethoxy) aluminum hydride [an English scientific name is sodium bis(2-methoxyethoxy)aluminum hydride, an English trade name is Red-Al, and Red-Al for short] is used as a catalyst for carrying out a ring-opening polymerization reaction of cycloate monomers (L-lactide L-LA, D, L-lactide, D, L-LA, glycolide GA, epsilon-caprolactone epsilon-CL, etc.) so as to synthesize a medical biodegradation material with high organism security. The use of stannous octoate catalysts which have cytotoxicity and are widely used at present is avoided by the new technological method. A bulk polymerization method is used by the technology, and the polymerization reaction has the characteristics of controllability and living polymerization, which not only can be used for synthesizing homopolymers, but also can be used for synthesizing block polymers with controlled components. The used catalyst Red-Al is a chemically pure reagent (a 70% toluene solution, namely an SCROS product), which has no poison. The technology has no three waste pollution and high economic benefit.
Description
Technical field
The present invention relates to a kind of medical use biological degradable, particularly relate to polyester material synthetic new process.(trade(brand)name: Red-Al is called for short: Red-Al) make catalyzer and carry out the monomeric ring-opening polymerization of cyclic ester (lactide, lactone) class, belong to technical field of polymer chemistry to use two (2-methoxyethoxy) sodium alanates.
Background technology
In recent years, because medicine and the fast development worldwide of bioengineered tissue science, the demand to medical biodegradable material rapidly increases both at home and abroad.(as poly (l-lactic acid) P (L-LA), poly-D, L-lactic acid P (D, L-LA), polyglycolic acid PGA, polycaprolactone (PCL) and interpolymer thereof etc.) is paid attention to most with aliphatic polyester at the medical biodegradable material of synthetic.Because this type of material has good biocompatibility, biological safety, thereby obtained extensive and important use, as: (1) is as controlled release drug carrier (as: anticancer and anti-AIDS target medicine carrier); (2) property implanted absorbable tissue engineering materials (as: operating sutures, bone engagement, immobilization material, artificial cartilage, ligament, tendon, blood vessel, ureter propping material etc.).At present both at home and abroad existing a more serious problem at this type of material aspect synthetic is: be used for polyreaction, be known as best commercial catalyst divalence stannide (as: the melt-polycondensation synthesizing polylactic acid of catalytic efficiency by market, the commercial catalyst tin protochloride and the tin protochloride-tosic acid of polyglycolic acid, ring-opening polymerization method synthesizing polylactic acid, the commercial catalyst stannous octoate of polyglycolic acid) has cytotoxicity, because can't be after the polyreaction with tin-containing 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 state natural sciences fund (No.20074016) is subsidized adopt the two medical degradation property polyester macromolecule of (2-methoxyethoxy) sodium alanate catalyzer synthesising biological materials 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, (lactide is as L-rac-Lactide L-LA with cyclic ester, D, L-rac-Lactide D, L-LA, glycollide GA, and lactone as: be that monomer is through ring-opening polymerization synthesis of medical biodegradable polyester material 6-caprolactone ε-CL etc.).
Two (2-methoxyethoxy) sodium alanate catalyst structures and chemical name and trade(brand)name are as follows:
Two (2-methoxyethoxy) sodium alanate
(Red-Al)
The characteristics beneficial effect of this law synthesis of medical biodegradable polymkeric substance is: productive rate height (〉=96%), polymer quality are good: number-average molecular weight Mn=1.0~4.0 * 10
4, color and luster is snow-white, narrow molecular weight distribution (PDI≤1.20).Polyreaction has the living polymerization characteristics, can be used for the segmented copolymer of the synthetic controlled composition of tool.This process using bulk polymerization, technology is simple, and the non-environmental-pollution thing generates.
Embodiment
1. be catalyzer with Red-Al, (L-rac-Lactide L-LA, D, L-rac-Lactide D, L-LA, glycollide GA, 6-caprolactone ε-CL etc.) are monomer with cyclic ester, obtain highly giving birth to body safe medical biodegradability polyester material through ring-opening polymerization.
2. medical use biological degradable polyester material synthesis technique: with cyclic ester class monomer (as: L-LA), Red-Al is (50~40,000) in molar ratio: 1.0 drop in the reactors, vacuumize to fill with high pure nitrogen after removing air again, so triplicate is closed reactor under the last vacuum.Reactor is under agitation slowly heated up, under steady temperature 100~200 ℃ then, (being preferably 110~130 ℃), reaction certain hour (24~120 hours).Behind the stopped reaction, with the polymkeric substance acetone solution, pour in the deionized water then and precipitate, at room temperature dry 24-72 hour of filtering water postprecipitation obtains the snowy white solid, is institute's synthesising biological degradation polymer.Medical biodegradable polymkeric substance building-up reactions formula is as follows:
R=H,CH
3 m=3,4,5
M
1, M
2Independently be selected from: LLA, DLLA, GA, ε-CL,
With the tetrahydrofuran (THF) is solvent, and μ-Styragel packed column measures institute's synthetic polymer molecule amount with the Waters-410 gel chromatograph under the room temperature, (be with the monodisperse polystyrene standard specimen and proofread and correct through pervasive value).Institute's synthetic polymer molecule amount can be controlled in Mn=1.0~4.0 * 10
4, molecular weight distributing index (PDI) is 1.10~1.40, productive rate 〉=96%, and product color is snow-white.
Embodiment 1
Pack in the reactor rac-Lactides of 144 grams, by monomer: catalyzer=10000: 1 (mol ratio) adds 1.0 milliliters of Red-Al toluene solutions, and (concentration is 1.0 * 10
-3Mol).Reactor is vacuumized, use the nitrogen replacement repetitive operation then three times, close reactor under the vacuum, reactor is slowly heated, (110~120 ℃) reaction certain hour is 72 hours under steady temperature.Behind the stopped reaction, reactor is chilled to room temperature, adds acetone solution still interpolymer then.Add deionized water then, polymer precipitation is come out.The filtering water places vacuum drying oven with precipitation at last, 50 ℃ of vacuum-dryings 24 hours, obtains the white powder solid, productive rate 99%.Polymericular weight is 2.0~4.0 * 10
4, PDI≤1.20.
Claims (1)
1. the method for two (2-methoxyethoxy) sodium alanate synthesis of medical biodegradable polyester materials, it is characterized in that: with two (2-methoxyethoxy) sodium alanates (Red-Al) is the medical use biological degradable polyester material that catalyzer carries out the monomeric body ring-opening polymerization of cyclic ester class synthesizing non-metal tin, cyclic ester class monomer is selected from D, L-rac-Lactide (DLLA), L-rac-Lactide (LLA), glycollide (GA), 6-caprolactone (ε-CL), the synthetic chemistry reaction formula is as follows:
R=H, CH
3M=5M
1Independently be selected from: LLA, DLLA, GA, M
2: independently be selected from: ε-CLn represents institute's synthesizing polyester number-average degree of polymerization, makes number-average molecular weight Mn=1.0~4.0 * 10 of polyester
4
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CN 200410018604 CN1238399C (en) | 2004-01-08 | 2004-01-08 | Technology method of synthesizing medical biodegradable material foom di(2-methoxy ethoxy) aluminium sodium hydride |
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CN1556129A CN1556129A (en) | 2004-12-22 |
CN1238399C true CN1238399C (en) | 2006-01-25 |
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