CN1156510C - Process for catalyzing ring-opening polymerization of lactide by 2-valence cyclopentadienyl rare-earth complex - Google Patents

Process for catalyzing ring-opening polymerization of lactide by 2-valence cyclopentadienyl rare-earth complex Download PDF

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CN1156510C
CN1156510C CNB011333502A CN01133350A CN1156510C CN 1156510 C CN1156510 C CN 1156510C CN B011333502 A CNB011333502 A CN B011333502A CN 01133350 A CN01133350 A CN 01133350A CN 1156510 C CN1156510 C CN 1156510C
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lactide
reaction
reaction bulb
solution
opening polymerization
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CN1359961A (en
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涛 唐
唐涛
崔冬梅
陈文启
黄葆同
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The present invention belongs to a process for catalyzing the ring-opening polymerization of a main body and a solution of lactide by a divalent cyclopentadienyl rare earth complex. In the process, the ring-opening polymerization of the lactide main body is carried out at 100 to 150 DEG C, and after 1 to 3 hours of the reaction, monomer conversion can reach 100%. A solvent used in the ring-opening polymerization of the lactide solution is tetrahydrofuran or toluene; in a tetrahydrofuran solution, the ring-opening polymerization of lactide can be carried out at room temperature to 70 DEG C, and after 3 to 15 hours of the reaction, monomer conversion can reach 100%. The ring-opening polymerization of lactide in a methylbenzene solution is carried out at 50 to 100 DEG C, and after 1 to 2 hours of the reaction, monomer conversion can reach 100%. The molecular weight of products is controlled by the molar ratio of a monomer to an initiator, and the configuration of obtained polylactide is maintained.

Description

The method of catalyzing ring-opening polymerization of lactide by 2-valence cyclopentadienyl rare-earth complex
Technical field: the method that the invention belongs to catalyzing ring-opening polymerization of lactide by 2-valence cyclopentadienyl rare-earth complex.Concrete relating to adopts polymerisation in bulk and polymerisation in solution implementation method to realize catalyzing ring-opening polymerization of lactide by 2-valence cyclopentadienyl rare-earth complex.
Background technology: polylactide is important a kind of in the aliphatic polyester, be that a class is biodegradable and have a material of biocompatibility, be widely used in medical equipment and replace the human body active material, can repair, repairing, replacing damaged or infected tissue or react to each other as interim skeleton or supporting (sutures, bone fixing part), interim obstacle (preventing tissue adhesion) with biosystem, the material of this perishability can hydrolysis and be degraded into the product that can be absorbed by the body and very little to the influence of organ, also can reduce the number of times of operation simultaneously; In field of pharmaceutical preparations as the dressing composition in slowly-releasing, controlled release or the targeting preparation.
The purposes of polyester material depends on its The Nomenclature Composition and Structure of Complexes.As propping material, require high molecular and high mechanical strength; And as medicinal film material, then tackling medicine has permeability.The The Nomenclature Composition and Structure of Complexes of material depends primarily on the catalyst system that synthesizes them.The polymerization of rac-Lactide is the alkoxy compound with tin, aluminium, zinc etc. the earliest, but because the polymerization mechanism decision, catalyzer is covalently bound on the chain of polymkeric substance, be difficult to be removed, this can pollute the environment of degraded, perhaps can cause accumulation in vivo, in particular for the medicine aspect, no matter require is polymkeric substance, degraded product, or the residue of catalyzer, all should be nontoxic.Iron is as the element that exists in the activity in vivo tissue, the polymerization that its compound can the catalysis rac-Lactide, and catalytic activity is lower, and polyreaction is carried out at 170-210 ℃ of high temperature, and racemization is obvious.
Rare earth compounding becomes the focus of Recent study because be easy to remove after polymerization is finished, but all catalysis rac-Lactide polymerizations of the system that rare earth alkoxide, rare earth aminate, rare earth aminate and rare earth compound-trialkylaluminium-water is formed.Macromolecules 1996.29,3332 have reported rare earth virtue oxygen complex, promptly three (2,6-di-t-butyl phenolic group) rare earth compound, catalyst system with various alcohol compositions, can make two kinds of lactone monomers make segmented copolymer, also can cause another kind of monomer with the performed polymer of hydroxy-functional and carry out block copolymerization through the substep addition method.And L-LA does not have ester exchange and configuration to transform generation in polymerization process.As with [2,6-(tBu) 2OAr] 3Ln (Ln=Y, La) catalyst system of (1a) forming with 2-PrOH (50/1) causes rac-Lactide, caprolactone, valerolactone respectively and is polymerized to example, in dichloromethane solvent, under the room temperature, monomer conversion reaches 85-90% within the several minutes, and number-average molecular weight equates with the theoretical value of calculating with the mol ratio of monomer/alcohol.Can the polymerization of catalysis rac-Lactide although mention catalyst system that various rare earth compound forms above, polymerization rate is slower, and temperature of reaction is higher, thereby makes product optically-active retention of configuration rate low.
Summary of the invention: the purpose of this invention is to provide with 2-valence cyclopentadienyl rare-earth complex catalysis rac-Lactide polymeric method.This method has the controllable polymerization feature, the characteristics that polymerization rate is fast, temperature of reaction is low.Gained polylactide molecular weight height, and retention of configuration.Simultaneously, the center rare earth ion is easy to remove from polymer product.The rare earth ion radius is big, and acidity is stronger, and the electronegativity of lactide monomer is very big, so rare earth compounding or compound are easy to and the lactide monomer coordination.
The cyclopentadienyl rare-earth complex that the present invention selects has following structure:
(1)
((R) mL) 2Ln(S) x
Wherein R is methyl, the tertiary butyl, pentamethylene base, trimethyl silicon based or 2-methoxy ethyl, and m=1 or 2, L are cyclopentadienyl, indenyl or fluorenyl; Ln is samarium or ytterbium, (S) xBe solvent, R 1Be ethyl-(CH 2CH 2)-, L 1And L 2Be cyclopentadienyl, indenyl or fluorenyl, L 1With L 2Can be identical, also can be different.
Technological process is as follows: levorotatory lactide is through 65 ℃ of pure systems of recrystallization of ethyl acetate, and rac-lactide is through 80 ℃ of pure systems of recrystallization of ethyl acetate.
Levorotatory lactide and outward turning rac-Lactide bulk polymerization: the bivalent rare earth half metallocene is a catalyzer, the mol ratio 100-3000 of monomer and catalyzer, the molar ratio of best monomer and catalyzer is 500-2500, temperature of reaction can be 110-210 ℃, best polymeric reaction temperature is 120-140 ℃, and the reaction times is 0.5-2 hour.
The solution polymerization process of levorotatory lactide and outward turning lactide: the solvent of employing is toluene or oxolane, monomer concentration is 15-50wt%, polymeric reaction temperature is 50-110 ℃, best polymeric reaction temperature is 60-100 ℃, the mol ratio of best monomer and catalyst is 300-2000, and the reaction time is 1-8 hour.Reaction finishes postcooling, and the chloroformic solution termination reaction with 10% hydrochloric acid obtains the faint yellow solid product.The specific rotation of levorotatory lactide polymkeric substance [α] wherein D 25=-123--149.
Method provided by the invention can prepare the high molecular polylactide of retention of configuration, and the polymeric temperature of reaction is lower, and side reaction is few, and polymerization rate is fast, has the characteristics of controllable polymerization, and the molecular weight of product is by the mol ratio control of monomer and initiator.
Embodiment:
Embodiment 1
Take by weighing 1.3g rac-lactide (D, L-LA) and (9mmol) in the reaction bulb of 40ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), reaction bulb is placed 120 ℃ constant temperature oil bath, treat that lactide dissolves rear adding ((CH 2CH 2(C 5H 9C 5H 3) 2) Sm (THF) solution 0.20ml (0.09M, 0.018mmol), [D, L-LA]/[((CH 2CH 2(C 5H 9C 5H 3) 2) Sm (THF))=500, reaction 0.5h places 0 ℃ frozen water to cool off reaction bulb, after the chloroformic solution of adding 1ml10% hydrochloric acid stops, pours sedimentation in the ethanol into, gets faint yellow solid, and vacuum drying 48h gets product 1.13g, conversion ratio 86.9%.Molecular weight with the gpc analysis polylactide gets Mn=2.7 ten thousand, Mw/Mn=1.88.
Embodiment 2
Take by weighing 1.0g levorotatory lactide (L-LA) and (7mmol) in the reaction bulb of 50ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), reaction bulb is placed 130 ℃ constant temperature oil bath, treat to add (C after the lactide melting 5H 9C 5H 4) 2Sm (DME) solution 0.1ml (0.07M, 0.007mmol), [L-LA]/[(C 5H 9C 5H 4) 2Sm (DME)]=1000, reaction 1h places 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48h gets product 1.0g, conversion ratio 100%.Molecular weight with the gpc analysis polylactide gets Mn=3.1 ten thousand, Mw/Mn=1.83.Specific rotation [α] D 25=-149.1 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 3
Take by weighing 2g levorotatory lactide (L-LA) and (14mmol) in the reaction bulb of 50ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), reaction bulb is placed 140 ℃ constant temperature oil bath, treat to add (C after the lactide melting 5H 9C 5H 4) 2Sm (DME) solution 0.08ml (0.07M, 0.0056mmol), [L-LA]/[(C 5H 9C 5H 4) 2Sm (DME)]=2500, reaction 2h places 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48h gets product 2.0g, conversion ratio 100%.Molecular weight with the gpc analysis polylactide gets Mn=5.3 ten thousand, Mw/Mn=2.53.Specific rotation [α] D 25=-132.8 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 4
Taking by weighing 1.0g levorotatory lactide (L-LA) (7mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 50ml with rubber tube, add 3ml toluene with syringe again, reaction bulb is placed 60 ℃ constant temperature oil bath, treat to add (C after the lactide melting 5H 9C 5H 4) 2Sm (DME) solution 0.2ml (0.07M, 0.014mmol), [L-LA]/[(C 5H 9C 5H 4) 2Sm (DME)]=500, reaction 1h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 1ml 10% hydrochloric acid stops, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum-drying 48h gets product 0.995g, transformation efficiency 99.5%.Molecular weight with the gpc analysis polylactide gets Mn=3.1 ten thousand, Mw/Mn=1.83.Specific rotation [α] D 25=-129.7 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 5
Taking by weighing 1.0g levorotatory lactide (L-LA) (7mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 50ml with rubber tube, add 2ml toluene with syringe again, reaction bulb is placed 80 ℃ constant temperature oil bath, treat to add (C after the lactide melting 5H 9C 5H 4) 2Yb (Et 2O) solution 0.35ml (0.04M, 0.014mmol), [L-LA]/[(C 5H 9C 5H 4) 2Yb (Et 2O)]=500, reaction 2h places 0 ℃ frozen water to cool off reaction bulb, after the chloroformic solution of adding 1mL10% hydrochloric acid stops, pours sedimentation in the ethanol into, gets flaxen spongy solid, and vacuum drying 48h gets product 0.93g, conversion ratio 93%.Molecular weight with the gpc analysis polylactide gets Mn=3.1 ten thousand, Mw/Mn=1.83.Specific rotation [α] D 25=-129.7 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 6
Taking by weighing 4.0g levorotatory lactide (L-LA) (28mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 50ml with rubber tube, add 4ml toluene with syringe again, reaction bulb is placed 60 ℃ constant temperature oil bath, treat to add (C after the lactide dissolving 5H 9C 9H 6) 2Sm (DME) solution 0.1ml (0.1213M, 0.014mmol), [L-LA]/[(C 5H 9C 9H 6) 2Sm (DME)]=2000, during reaction 2h, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48h gets product 3.4g, conversion ratio 85%.Molecular weight with the gpc analysis polylactide gets Mn=7.4 ten thousand, Mw/Mn=2.50.Specific rotation [α] D 25=-133.5 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 7
Taking by weighing 1.5g levorotatory lactide (L-LA) (10.5mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 50ml with rubber tube, add 6ml toluene with syringe again, reaction bulb is placed 80 ℃ constant temperature oil bath, treat to add ((CH after the lactide dissolving 3) 3SiC 5H 4) 2Sm (DME) 0.20ml (0.067M, 0.014mmol), [L-LA]/[((CH 3) 3SiC 5H 4) 2Sm (DME)]=800, reaction 3h places 0 ℃ frozen water to cool off reaction bulb, after the chloroformic solution of adding 1ml 10% hydrochloric acid stops, pours sedimentation in the ethanol into, gets flaxen spongy solid, and vacuum drying 48h gets product 1.23g, conversion ratio 82%.Molecular weight with the gpc analysis polylactide gets Mn=6.3 ten thousand, Mw/Mn=1.71.Specific rotation [α] D 25=-146.8 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 8
Taking by weighing 2.0g levorotatory lactide (L-LA) (14mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 50ml with rubber tube, add 10ml toluene with syringe again, reaction bulb is placed 90 ℃ constant temperature oil bath, treat to add (C after the lactide dissolving 6H 5CH 2C 9H 6) 2Sm (DME) solution 0.14ml (0.1027M, 0.014mmol), [L-LA]/[(C 6H 5CH 2C 9H 6) 2Sm (DME)]=1000, reacted 2 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48 hours gets product 1.68g, conversion ratio 84%.Molecular weight with the gpc analysis polylactide gets Mn=7.8 ten thousand, Mw/Mn=2.0.Specific rotation [α] D 25=-138.7 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 9
Taking by weighing 1.3 gram levorotatory lactides (L-LA) (9.1mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 50ml with rubber tube, add 6ml toluene with syringe again, reaction bulb is placed 85 ℃ constant temperature oil bath, treat to add ((CH after the lactide dissolving 3) 2Si (C 5H 4) 2) Sm (THF) solution 0.20ml (0.038M, 0.014mmol), [L-LA]/[((CH 3) 2Si (C 5H 4) 2) Sm (THF)]=600, reacted 3 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48 hours gets product 1.23g, conversion ratio 82%.Molecular weight with the gpc analysis polylactide gets Mn=6.3 ten thousand, Mw/Mn=1.71.Specific rotation [α] D 25=-146.8 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 10
Taking by weighing 1.1 gram levorotatory lactides (L-LA) (7.6mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 40ml with rubber tube, add 4.5ml toluene with syringe again, reaction bulb is placed 70 ℃ constant temperature oil bath, treat to add ((CH after the lactide dissolving 3) 3CC 5H 4) 2Sm (THF) solution 0.18ml (0.042M, 0.0076mmol), [L-LA]/[((CH 3) 3CC 5H 4) 2Sm (THF)]=1000, reacted 2.5 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48 hours gets product 1.0g, conversion ratio 90.1%.Molecular weight with the gpc analysis polylactide gets Mn=10.4 ten thousand, Mw/Mn=2.0.Specific rotation [α] D 25=-139.7 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 11
Taking by weighing 2.13 gram levorotatory lactides (L-LA) (14.7mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 40ml with rubber tube, add 7ml toluene with syringe again, reaction bulb is placed 100 ℃ constant temperature oil bath, treat to add ((CH after the lactide dissolving 3) 3CC 5H 4) 2Yb (THF) solution 0.23ml (0.043M, 0.0098mmol), [L-LA]/[((CH 3) 3CC 5H 4) 2Yb (THF)]=1500, reacted 1.5 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48 hours gets product 1.98g, conversion ratio 93%.Molecular weight with the gpc analysis polylactide gets Mn=11.3 ten thousand, Mw/Mn=2.3.Specific rotation [α] D 25=-136.2 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 12
Taking by weighing 1.65 gram levorotatory lactides (L-LA) (11.45mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 40ml with rubber tube, add 10ml toluene with syringe again, reaction bulb is placed 90 ℃ constant temperature oil bath, treat to add ((CH after the lactide dissolving 3) 3CC 9H 6) 2Sm (THF) solution 0.10ml (0.164M, 0.0164mmol), [L-LA]/[((CH 3) 3CC 9H 6) 2Sm (THF)]=700, reacted 3 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48 hours gets product 1.47g, conversion ratio 89%.Molecular weight with the gpc analysis polylactide gets Mn=6.2 ten thousand, Mw/Mn=1.89.Specific rotation [α] D 25=-135.4 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 13
Taking by weighing 1.4 gram levorotatory lactides (L-LA) (9.7mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 40ml with rubber tube, add 3.0ml toluene with syringe again, reaction bulb is placed 60 ℃ constant temperature oil bath, treat to add (CH after the lactide dissolving 3OCH 2CH 2C 5H 4) 2Sm (THF) solution 0.22ml (0.055M, 0.012mmol), [L-LA]/[(CH 3OCH 2CH 2C 5H 4) 2Sm (THF)]=800, reacted 2 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get flaxen spongy solid, vacuum drying 48 hours gets product 1.2g, conversion ratio 85.7%.Molecular weight with the gpc analysis polylactide gets Mn=7.2 ten thousand, Mw/Mn=2.1.Specific rotation [α] D 25=-133.4 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 14
Take by weighing 1.3 gram rac-lactide (D, L-LA) (9mmol) in the reaction bulb of 40ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), add 6.5ml toluene with syringe again, reaction bulb is placed 65 ℃ constant temperature oil bath, treat to add (CH after the lactide dissolving 3OCH 2CH 2C 9H 6) 2Sm (THF) solution 0.15ml (0.086M, 0.0129mmol), [D, L-LA]/[(CH 3OCH 2CH 2C 9H 6) 2Sm (THF)]=700, reacted 2 hours, place 0 ℃ frozen water to cool off reaction bulb, after the chloroformic solution of adding 1ml 10% hydrochloric acid stops, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 1.0g, conversion ratio 76.9%.Molecular weight with the gpc analysis polylactide gets Mn=5.7 ten thousand, Mw/Mn=1.84.
Embodiment 15
Take by weighing 1.7 gram rac-lactide (D, L-LA) (11.8mmol) in the reaction bulb of 40ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), add 8ml toluene with syringe again, reaction bulb is placed 85 ℃ constant temperature oil bath, treat to add (CH after the lactide dissolving 2CH 2(C 9H 6) 2) Sm (THF) solution 0.28ml (0.11M, 0.0295mmol), [D, L-LA]/[(CH 2CH 2(C 9H 6) 2) Sm (THF)]=400, reacted 1.5 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 1.31g, conversion ratio 76.9%.Molecular weight with the gpc analysis polylactide gets Mn=3.2 ten thousand, Mw/Mn=1.71.
Embodiment 16
Take by weighing 2.1 gram rac-lactide (D, L-LA) (14.6mmol) in the reaction bulb of 40ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), add 6ml toluene with syringe again, reaction bulb is placed 85 ℃ constant temperature oil bath, treat to add (CH after the lactide dissolving 3OCH 2CH 2C 9H 6) 2Yb (THF) solution 0.17ml (0.286M, 0.0487mmol), [D, L-LA]/[(CH 3OCH 2CH 2C 9H 6) 2Yb (THF)]=300, reacted 1 hour, place 0 ℃ frozen water to cool off reaction bulb, after the chloroformic solution of adding 1ml 10% hydrochloric acid stops, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 1.82g, conversion ratio 86.6%.Molecular weight with the gpc analysis polylactide gets Mn=2.3 ten thousand, Mw/Mn=1.65.
Embodiment 17
Take by weighing 2.3 gram rac-lactide (D, L-LA) (16mmol) in the reaction bulb of 40ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), add 5ml toluene with syringe again, reaction bulb is placed 100 ℃ constant temperature oil bath, treat to add (C after the lactide dissolving 5H 9C 5H 4) Sm (C 5H 9C 9H 6) (THF) solution 1.33ml (0.04M, 0.0533mmol), [D, L-LA]/[(C 5H 9C 5H 4) Sm (C 5H 9C 9H 6) (THF)]=300, reacted 1.5 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 2.1g, conversion ratio 91.3%.Molecular weight with the gpc analysis polylactide gets Mn=1.4 ten thousand, Mw/Mn=1.55.
Embodiment 18
Taking by weighing 1.56 gram levorotatory lactides (L-LA) (10.82mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 40ml with rubber tube, add 2.2ml toluene with syringe again, reaction bulb is placed 70 ℃ constant temperature oil bath, treat to add (CH after the lactide dissolving 2CH 2(C 5H 9C 5H 3) 2) Sm (THF) solution 0.22ml (0.061M, 0.0135mmol), [L-LA]/[(CH 2CH 2(C 5H 9C 5H 3) 2) Sm (THF)]=800, reacted 1.5 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 1.50g, conversion ratio 96.2%.Molecular weight with the gpc analysis polylactide gets Mn=6.01 ten thousand, Mw/Mn=2.14.Specific rotation [α] D 25=-141.7 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 19
Taking by weighing 0.97 gram levorotatory lactide (L-LA) (6.73mmol) (processes for three times through the roasting cooling of fire argon filling) in the reaction bulb of 40ml with rubber tube, add 1.0ml toluene with syringe again, reaction bulb is placed 60 ℃ constant temperature oil bath, treat to add (CH after the lactide dissolving 2CH 2(C 5H 9C 5H 3) 2) Yb (THF) solution 0.188ml (0.072M, 0.0135mmol), [L-LA]/[(CH 2CH 2(C 5H 9C 5H 3) 2) Yb (THF)]=500, reacted 3 hours, place 0 ℃ frozen water to cool off reaction bulb, after adding the chloroformic solution termination of 1ml 10% hydrochloric acid, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 0.75g, conversion ratio 77.3%.Molecular weight with the gpc analysis polylactide gets Mn=2.99 ten thousand, Mw/Mn=1.68.Specific rotation [α] D 25=-140.5 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 20
Take by weighing 1.5 gram levorotatory lactides (L-LA) (10.5mmol) in the reaction bulb (through fire roasting cooling argon filling three time process) of 50ml with rubber tube, add 5ml THF with syringe again, reaction bulb is placed 50 ℃ constant temperature oil bath, treat that lactide dissolves rear adding (C fully 5H 9C 5H 4) 2Sm (DME) solution 0.5ml (0.07M, 0.035mmol), [L-LA]/[(C 5H 9C 5H 4) 2Sm (DME)]=300, reacted 3 hours, place 0 ℃ frozen water to cool off reaction bulb, after the chloroformic solution of adding 1ml 10% hydrochloric acid stops, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 1.24g, conversion ratio 83%.Molecular weight with the gpc analysis polylactide gets Mn=1.26 ten thousand, Mw/Mn=1.57.Specific rotation [α] D 25=-123.1 (25 ℃, the 0.025g/25ml chloroform).
Embodiment 21
Take by weighing 1.42 gram rac-lactide (D, L-LA) (9.85mmol) in the reaction bulb of 40ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), add 3 oxolanes with syringe again, reaction bulb is placed 60 ℃ constant temperature oil bath, treat to add (C after the lactide dissolving 5H 9C 5H 4) Sm (C 13H 11) (THF) solution 3.1ml (0.053M, 0.0164mmol), [D, L-LA]/[(C 5H 9C 5H 4) Sm (C 13H 11) (THF)]=600, reacted 6 hours, after the chloroformic solution of adding 1ml 10% hydrochloric acid stops, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 0.7g, conversion ratio 49.3%.Molecular weight with the gpc analysis polylactide gets Mn=1.9 ten thousand, Mw/Mn=1.46.
Embodiment 22
Take by weighing 3.90g rac-lactide (D, L-LA) (27mmol) in the reaction bulb of 40ml with rubber tube, (process for three times through the roasting cooling of fire argon filling), add 1.5ml toluene with syringe again, reaction bulb is placed 60 ℃ constant temperature oil bath, treat to add (C after the lactide dissolving 5H 9C 5H 4) Yb (C 5H 9C 9H 6) (THF) solution 0.23ml (0.066M, 0.015mmol), [D, L-LA]/[(C 5H 9C 5H 4) Yb (C 5H 9C 9H 6) (THF)]=1800, reacted 8 hours, place 0 ℃ frozen water to cool off reaction bulb, after the chloroformic solution of adding 1ml 10% hydrochloric acid stops, pour sedimentation in the ethanol into, get faint yellow solid, vacuum drying 48 hours gets product 3.16g, conversion ratio 81%.Molecular weight with the gpc analysis polylactide gets Mn=5.2 ten thousand, Mw/Mn=1.87.

Claims (1)

  1. A kind of method of catalyzing ring-opening polymerization of lactide by 2-valence cyclopentadienyl rare-earth complex is characterized in that the cyclopentadienyl rare-earth complex of selecting has following structure:
    (1)
    ((R) mL) 2Ln(S) x
    Figure C0113335000021
    Wherein R is methyl, the tertiary butyl, pentamethylene base, trimethyl silicon based or 2-methoxy ethyl, and m=1 or 2, L are cyclopentadienyl, indenyl or fluorenyl; Ln is samarium or ytterbium, (S) xBe solvent, R 1Be ethyl-(CH 2CH 2)-, L 1And L 2Be cyclopentadienyl, indenyl or fluorenyl, L 1With L 2Can be identical, also can be different;
    Technological process is as follows:
    Levorotatory lactide and outward turning rac-Lactide bulk polymerization: the bivalent rare earth half metallocene is a catalyzer, the mol ratio 100-3000 of monomer and catalyzer, and temperature of reaction is 110-210 ℃, the reaction times is 0.5-2 hour;
    The solution polymerization process of levorotatory lactide and outward turning rac-Lactide: the solvent of employing is toluene or tetrahydrofuran (THF), and monomer concentration is 15-50wt%, and polymeric reaction temperature is 50-110 ℃, and the mol ratio of monomer and catalyzer is 300-2000, and the reaction times is 1-8 hour;
    Reaction finishes postcooling, and the chloroformic solution termination reaction with 10% hydrochloric acid obtains the faint yellow solid product; The specific rotation of levorotatory lactide polymkeric substance [α] wherein D 25=-123--149.
CNB011333502A 2001-10-26 2001-10-26 Process for catalyzing ring-opening polymerization of lactide by 2-valence cyclopentadienyl rare-earth complex Expired - Fee Related CN1156510C (en)

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CN1305864C (en) * 2004-05-31 2007-03-21 安徽师范大学 Bivalent rare earth complex containing oxacyclo substituted indene ligand and its use
CN101443343B (en) * 2006-05-09 2014-11-12 独立行政法人理化学研究所 Metallocene complex and polymerization catalyst composition containing the same
CN101343354B (en) * 2008-08-29 2011-05-04 胡权 Poly-lactide, poly-glycolide and preparation for copolymer of the same
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