CN1806919A - Use of stannous benzoate as catalyst - Google Patents
Use of stannous benzoate as catalyst Download PDFInfo
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- CN1806919A CN1806919A CNA2006100492887A CN200610049288A CN1806919A CN 1806919 A CN1806919 A CN 1806919A CN A2006100492887 A CNA2006100492887 A CN A2006100492887A CN 200610049288 A CN200610049288 A CN 200610049288A CN 1806919 A CN1806919 A CN 1806919A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides the usage of using the benzoic acid stannous as catalyst. The invention solves the problem that polymerization rate of current catalyst in lactic acid and glycolic acid is slow. The benzoic acid stannous is the catalyst used for preparing low-molecular polymer lactic acid with lactic acid dewatering; benzoic acid stannous is the catalyst used for preparing lactide with low-molecular polymer lactic acid cracking; benzoic acid stannous is the catalyst used for preparing polylactic acid with lactide polymerizing; benzoic acid stannous is the catalyst used for preparing low-molecular polymer glycolic acid with glycolic acid dewatering; benzoic acid stannous is the catalyst used for preparing glycolide with low-molecular polymer glycolic acid cracking; benzoic acid stannous is the catalyst used for preparing poly-glycollide with glycolide polymerizing. The benzoic acid stannous is the catalyst used for polymerizing glycolide, lactide and epsilon-caprolactone. Using the benzoic acid stannous is low content, high productivity, high product purity, low temperature and good repeatability.
Description
Technical field
The present invention relates to benzoic acid stannous purposes, relate in particular to benzoic acid stannous purposes in catalyst field.
Background technology
Catalyst is meant in chemical reaction can change reaction rate, and the material that quality of itself and chemical composition all do not change before and after reaction; Under the effect of catalyst, can reduce reaction temperature, time and pressure greatly.
Lactic acid or glycolic acid form molecular weight at 2000～10000 oligomer through dehydration under catalyst action, directly cracking decompression distillation at high temperature obtains crude lactide or thick glycolide subsequently.Lactic acid commonly used or glycolic acid dehydration are oligomeric to be had with catalyst Pintsch process: AlCl
3, FeCl
3, FeCl
2, BF
3, BBr
3, TiO
2, TiCl
4, TiBr
4, SnSO
4, SnBr
4, stannous octoate etc.Use these catalyst easily to make the coking in cracking reactor of lactic acid oligomer or glycolic acid oligomers become piece, be difficult to cleaning, and every reaction one less important cleaning once, consume great amount of manpower and material resources; Lactide that obtains in addition or the jaundice of glycolide color, and yield is lower;
The catalyst that the ring-opening polymerisation of lactone and lactide is adopted usually has aluminium isopropoxide, stannous octoate and organic rare earth compounds etc., and wherein using the most extensive is stannous octoate, but its nontoxic synthetic high polymer and the good polyester of optical purity.But its catalytic reaction activity is not high, requires long polymerization reaction time and higher reaction temperature; Therefore need a kind of highly active polymerization catalyst of exploitation.
Summary of the invention
It is slow at lactic acid and glycolic acid oligomerization rate to the present invention is directed to existing catalyst, make product coking in reactor become piece in the cracking reaction process easily, the product color jaundice that obtains, and the lower shortcoming of yield are so provide benzoic acid stannous as oligomeric and purposes catalyst for cracking.
The present invention also ring-opening polymerization activity at existing catalyst lactide and cyclic ester is not high, requires long polymerization reaction time and higher reaction temperature, so benzoic acid stannous purposes as the high activity polymerization catalyst is provided.
In fact, the present invention relates to the benzoic acid stannous purposes that forms the catalyst of lact-acid oligomer as acid by dehydrating lactic.
As preferably: described lactic acid is L-lactic acid, D-lactic acid, D, one or more mixing in the L-lactic acid.
Relate to the benzoic acid stannous purposes that generates the catalyst of lactide as the lact-acid oligomer cracking.
Relate to the benzoic acid stannous purposes that becomes the catalyst of PLA as lactide homopolymerization symphysis.
As preferably, described lactide is the L-lactide, D-lactide, meso D, one or more mixing in the L-lactide; Wherein said equal polymerization method is a kind of in polymerisation in bulk or the polymerisation in solution.
The catalyst of benzoic acid stannous and Pintsch process oligomeric as acid by dehydrating lactic, reactivity height, lactide productive rate height.Lactic acid (88% aqueous solution) obtains polygalacto acid oligomer (molecular weight is generally 1000～3000) after the esterification through dehydration and adds that benzoic acid stannous (consumption is 0.1～0.2wt%) as catalyst, can shorten acid by dehydrating lactic and oligomer reaction time, generally can reduce 5～6 hours reaction time at 180～240 ℃ of cracking generation lactides.Catalyst is reusable, noncoking in the reactor.As lactide ring-opening polymerization catalyst, reaction temperature is identical with stannous octoate, is applicable to the polymerisation in bulk and the polymerisation in solution of lactide, contains residual monomer in polymerisation in bulk in the polymer, when characterize polymers, residual monomer must be removed; Polymerisation in solution is a solvent with toluene, with ethanol as precipitating reagent, but with polymer separate out, the calculated yield of weighing after the drying and to polymer characterization.Bulk polymer can be used the nmr for the determination conversion ratio, but polymer must be separated out, could be characterized polymer after the drying, as determining molecular weight etc. with ethanol again after with dissolution with solvents.Product is that polylactide is also referred to as PLA, has biodegradability.As plastics, its performance and polypropylene are similar, can reach poly serviceability by modification, therefore, are widely used in the preparation of various plastic products.Processing methods such as PLA itself or be applicable to by physical modification common is extruded, injection, blown film, foaming, plastic uptake.Fiber, film, rod, piece, sheet material etc. be can make and various civilian, commercial Application such as weaving, packing and medical special application field are applied to.
Because lactic acid has the existence of a methyl on the α position, make lactic acid have optical activity, so there is the mixture of left-handed (L), two kinds of optical isomers of dextrorotation (D) and DL different proportion in lactic acid, and wherein L type and 1: 1 mixture of D type are called D, L-lactic acid.The dimer lactide that lactide (LA) is made up of the acid by dehydrating lactic cyclisation of two molecules is to form the low PLA of molecular weight via acid by dehydrating lactic, obtains through the Pintsch process decompression distillation again.Because the existence of two kinds of optical isomers of lactic acid, the left-handed-lactide (LLA) that causes lactide to exist, dextrorotation-lactide (DLA) and three kinds of isomers of Study of Meso-Lactide (meso-DLLA) and the mixture of different proportion between them.The mixture of left-handed-lactide of 50% and dextrorotation-lactide of 50% is called as rac-lactide (racemic-DLLA).
Therefore, used lactic acid can be L-lactic acid, D-lactic acid, D, one or more mixing in the L-lactic acid among the present invention.Resulting lactide is the L-lactide, D-lactide, meso D, one or more mixing in the L-lactide.Common L-lactic acid, D-lactic acid polarimetry purity is 95～99.5%.
In addition, the invention still further relates to the benzoic acid stannous purposes that generates the catalyst of oligomeric hydroxy acetate as glycolic acid dehydration.
Also relate to the benzoic acid stannous purposes that generates the catalyst of glycolide as the cracking of oligomeric hydroxy acetate.
Also relate to the benzoic acid stannous purposes that becomes the catalyst of poly-glycolide as glycolide homopolymerization symphysis.Describedly all be polymerized to a kind of in polymerisation in bulk or the polymerisation in solution.
The purposes that also relates to benzoic acid stannous catalyst as the combined polymerization between glycolide, lactide, 6-caprolactone both or the three.
As preferably, described lactide is the L-lactide, D-lactide, D, one or more mixing in the L-lactide; Wherein said process for copolymerization is a kind of in polymerisation in bulk or the polymerisation in solution.
The catalyst of benzoic acid stannous and Pintsch process oligomeric as glycolic acid dehydration, characteristics are that catalyst amount is low, the reactivity height, glycolide yield height, the product purity height, color is white, and cracking temperature is low, and is reusable.As glycolide ring-opening polymerization catalyst, characteristics are polymerization rate gentlenesses, and product melt index height is applicable to polymerisation in solution or polymerisation in bulk.When adopting polymerisation in solution, because poly-glycolide is not dissolved in common organic solvent, therefore, the polymerization deposited phenomenon takes place.Poly-glycolide only is dissolved in the perfluor isopropyl alcohol.Benzoic acid stannous as the copolymerization catalyst between both or the three between glycolide, lactide, the 6-caprolactone, characteristics are polymerization activity height, the molecular weight height of polymer, be applicable to polymerisation in bulk, in addition, according to the content that feeds intake of glycolide,, then can adopt polymerisation in solution if polymerizate can be dissolved in the organic solvent.
The main chain of biodegradable polyesters is to be formed by connecting by the ester bond of aliphatic structure unit by facile hydrolysis, hydrolysis under the promotion of microorganism or organism enzyme or acid, alkali, molecular weight reduces, final carbon dioxide and the water of forming, the good tissue compatibility is arranged simultaneously, be widely used in the medical surgery sutures, fixing in the fracture, organizational project repair materials and controlled drug delivery system etc.
Polyglycolic acid or to be called poly-glycolide (PGA) be the simplest linear aliphatic adoption of structure ester is to absorb the commercial the earliest kind of macromolecule in the body.Having made HMW respectively by lactide (LA) and glycolide (GA) ring-opening polymerisation gets PLA or is called polylactide (PLA) and poly-glycolide (PGA), because its easy hydrolysis, and the product of degraded is that lactic acid, glycolic acid etc. all are the intermediate products of organism metabolism, is replaced collagen so this kind polyester pays the utmost attention to as degradable sutures.Subsequently, the ring-opening polymerisation of cyclic ester class has obtained extensive studies.Degradation speed is improved more than 10 times than homopolymer, and, can regulate the degradation rate of copolymer effectively by changing the ratio of component of glycolide and lactide.The copolymer of glycolide and lactide can be used as cancer therapy drug control delivery systme base material and makes the new sustained release medicine, equally, glycolide, lactide also are functional materials such as interim reparation, medicament slow release in good tissue engineering rack, operation stitching thing, the body with the copolymer of 6-caprolactone monomer.
Therefore the present invention has the following advantages:
1, the present invention relates to the catalyst of benzoic acid stannous and cracking oligomeric as lactic acid, have catalyst amount low (only be 0.05～1wt%), yield height (85～95%), the product purity height, color is white, cracking temperature is low, reusable characteristics.
2, the present invention relates to benzoic acid stannous catalyst as the lactide ring-opening polymerisation, have the polymerization rate gentleness, the molecular weight of product height is suitable for the characteristics of polymerisation in solution and polymerisation in bulk.
3, the present invention relates to the catalyst of benzoic acid stannous and Pintsch process oligomeric as glycolic acid dehydration, it is low to have a catalyst amount, the reactivity height, and glycolide yield height, the product purity height, color is white, and cracking temperature is low, reusable characteristics.
4, the benzoic acid stannous catalyst as the glycolide ring-opening polymerization that the present invention relates to has the polymerization rate gentleness, and product melt index height is applicable to the characteristics of polymerisation in solution or polymerisation in bulk.
5, the benzoic acid stannous catalyst as the combined polymerization between both or the three between glycolide, lactide, the 6-caprolactone that the present invention relates to has the polymerization activity height, and the molecular weight height of polymer is applicable to the characteristics of polymerisation in bulk or polymerisation in solution.
The specific embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail; But the present invention is not limited to these embodiment.
Embodiment 1
The L-lactic acid aqueous solution (concentration is 88wt%) that takes by weighing 10Kg is put into 10 liters of there-necked flasks, adds the benzoic acid stannous catalyst of 30g (0.3wt%), decompression, heat up and dewater, dehydration temperaturre is controlled at 120～180 ℃, the later stage decompression dehydration, form oligomer, finish reaction in 8 hours.Switch receiving device, collect the L-lactide 180～240 ℃ of decompression cracking, 6h finishes, and obtains thick L-lactide 6.5Kg, and product yield 92%, product fusing point are 94 ℃.
Embodiment 2
The L-lactic acid aqueous solution (concentration is 88wt%) that takes by weighing 10Kg is put into 10 liters of there-necked flasks, adds the benzoic acid stannous catalyst of 5g (0.05wt%), decompression, heat up and dewater, dehydration temperaturre is controlled at 120～180 ℃, the later stage decompression dehydration, form oligomer, finish reaction in 10 hours.Switch receiving device, collect the L-lactide 180～240 ℃ of decompression cracking, 8h finishes, and obtains thick L-lactide 6.2Kg, and product yield 88%, product fusing point are 93 ℃.
Embodiment 3
The L-lactic acid aqueous solution (concentration is 88wt%) that takes by weighing 10Kg is put into 10 liters of there-necked flasks, adds the benzoic acid stannous catalyst of 100g (1wt%), decompression, heat up and dewater, dehydration temperaturre is controlled at 120～180 ℃, the later stage decompression dehydration, form oligomer, finish reaction in 7 hours.Switch receiving device, collect the L-lactide 180～240 ℃ of decompression cracking, 5h finishes, and obtains thick L-lactide 6.6Kg, and product yield 94%, product fusing point are 94 ℃.
Embodiment 4
The D-lactic acid aqueous solution (concentration is 88wt%) that takes by weighing 1Kg is put into 3 liters of there-necked flasks, adds the benzoic acid stannous catalyst of 3g (0.3wt%), decompression, heat up and dewater, dehydration temperaturre is controlled at 120～180 ℃, the later stage decompression dehydration, form oligomer, finish reaction in 8 hours.Switch receiving device, collect the L-lactide 180～240 ℃ of decompression cracking, 6h finishes, and obtains thick D-lactide 0.64Kg, and product yield 91%, product fusing point are 94 ℃.
Embodiment 5
Operating procedure is identical with embodiment 1, and wherein with D, L-lactic acid replaces with L-lactic acid.Obtain thick D, L-lactide 6.1Kg, product yield are 87%, and the product fusing point is 52 ℃.
Embodiment 6
The lactide that obtains in the foregoing description is obtained the polymer grade lactide through decompression distillation or the purification of ethyl acetate solvent recrystallization, wherein polymer grade D-lactide, polymer grade L-lactide fusing point are 97～98 ℃, polymer grade meso D, L-lactide fusing point is 52 ℃, polymer grade racemic D, L-lactide fusing point is 126～128 ℃.
Under the condition of anhydrous and oxygen-free, get polymer grade L-lactide 6.0Kg, be heated to 110 ℃ of thawings after, join in 10 liters of reactors of vacuum drying, then, add benzoic acid stannous 3g (0.05wt%), the incipient stage, temperature of reaction kettle is controlled at 110～125 ℃ of stirrings and carries out polymerisation, about 4～6 hours, the system viscosity increased, and stopped to stir, constantly heat release in the course of reaction, the control temperature in the kettle.Rising reaction temperature to 130 ℃ continues reaction 48 hours, and reaction temperature to the temperature in the kettle that begins then to raise is 190 ℃, use nitrogen pressure 2.5Mpa, begins discharging, by tie rod, water-cooled, pelletizing, collection pellet.The viscosity-average molecular weight of the poly-L-lactide that obtains is 7.7 ten thousand, under 190 ℃, and capillary diameter 1.095mm, under the pressure of 2.16kg, the index of the fusion of product is 6.2g/10min.
Embodiment 7
Under the condition of anhydrous and oxygen-free, get polymer grade L-lactide 6.0Kg, be heated to 110 ℃ of thawings after, join in 10 liters of reactors of vacuum drying, then, add benzoic acid stannous 0.6g (0.01wt%), the incipient stage, temperature of reaction kettle is controlled at 110～125 ℃ of stirrings and carries out polymerisation, about 6～8 hours, the system viscosity increased, and stopped to stir, constantly heat release in the course of reaction, the control temperature in the kettle.Rising reaction temperature to 130 ℃ continues reaction 72 hours, and the reaction temperature that raises then to temperature in the kettle is 190 ℃, use nitrogen pressure 2.5Mpa, begins discharging, by tie rod, water-cooled, pelletizing, collection pellet.The viscosity-average molecular weight of the poly-L-lactide that obtains is 15.6 ten thousand, under 190 ℃, and capillary diameter 1.095mm, under the pressure of 2.16kg, the index of the fusion of product is 3.6g/10min.
Embodiment 8
Under the condition of anhydrous and oxygen-free, get polymer grade L-lactide 6.0Kg, be heated to 110 ℃ of thawings after, join in 10 liters of reactors of vacuum drying, then, add benzoic acid stannous 6g (0.1wt%), the incipient stage, temperature of reaction kettle is controlled at 110～125 ℃ of stirrings and carries out polymerisation, about 2～4 hours, the system viscosity increased, and stopped to stir, constantly heat release in the course of reaction, the control temperature in the kettle.Rising reaction temperature to 130 ℃ continues reaction 24 hours, and the reaction temperature that raises then to temperature in the kettle is 180 ℃, use nitrogen pressure 2.5Mpa, begins discharging, by tie rod, water-cooled, pelletizing, collection pellet.The viscosity-average molecular weight of the poly-L-lactide that obtains is 4.3 ten thousand, under 180 ℃, and capillary diameter 1.095mm, under the pressure of 2.16kg, the index of the fusion of product is 16.2g/10min.
Embodiment 9
Operating procedure is identical with embodiment 7, with polymer grade meso D, the L-lactide substitutes polymer grade L-lactide, the poly-D that obtains, the GPC number-average molecular weight of L-lactide is 7.4 ten thousand, molecular weight distribution is 3.24, under 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the index of the fusion of product is 8.2g/10min.
Embodiment 10
Under the condition of anhydrous and oxygen-free, get benzoic acid stannous 0.03g (0.05wt%), polymer grade D-lactide 60g, join in the glass reaction bottle of 150ml, then, the incipient stage, control reaction temperature at 120～125 ℃ with oil bath, magnetic agitation is carried out polymerisation, and about 6～8 hours, the system viscosity increased, stop to stir, rising reaction temperature to 130 ℃ continues reaction 72 hours, polymerizate, add the chloroform dissolving, separate out with ethanol, drying obtains poly-D-lactide, and its viscosity-average molecular weight is 14.8 ten thousand, under 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the index of the fusion of product is 4.9g/10min.
Embodiment 11
Under the condition of anhydrous and oxygen-free, get benzoic acid stannous 0.03g (0.05wt%), polymer grade D, L-lactide 60g joins in the glass reaction bottle of 150ml, then, incipient stage, at 130～150 ℃, magnetic agitation is carried out polymerisation with oil bath control reaction temperature, about 4～6 hours, the system viscosity increased, and stopped to stir, rising reaction temperature to 140 ℃ continues reaction 48 hours, polymerizate, add the chloroform dissolving, separate out with ethanol, drying obtains poly-D, L-lactide, the GPC number-average molecular weight is 8.3 ten thousand, molecular weight distribution is 2.85, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the index of the fusion of product is 6.9g/10min.
Embodiment 12
Under the condition of anhydrous and oxygen-free, get polymer grade D-lactide 20g and polymer grade L-lactide 80g, benzoic acid stannous 0.05g (0.05wt%) joins in the glass reaction bottle of 250ml, then, incipient stage, at 120～125 ℃, magnetic agitation is carried out polymerisation with oil bath control reaction temperature, about 4～6 hours, the system viscosity increases, and stops to stir rising reaction temperature to 130 ℃, continue reaction 48 hours, polymerizate adds the chloroform dissolving, separates out with ethanol, drying obtains poly-D, L-lactide, GPC number-average molecular weight are 7.6 ten thousand, and molecular weight distribution is 2.92, under 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the index of the fusion of product is 8.7g/10min.
Embodiment 13
Under the condition of anhydrous and oxygen-free, get polymer grade L-lactide 2.0Kg, after being heated to 110 ℃ of thawings, join in 10 liters of reactors of vacuum drying, then, add 5 liters of xylene solvents containing benzoic acid stannous 1g (0.05wt%), the incipient stage, temperature of reaction kettle is controlled at 120～125 ℃ of stirrings and carries out polymerisation, after 6 hours, the system viscosity increases, constantly heat release in the course of reaction, then, rising reaction temperature to 130 ℃ continues reaction 72 hours, and the solution of polymer is collected in the porcelain enamel barrel, use precipitation with alcohol, the viscosity-average molecular weight of the poly-L-lactide that drying obtains is 15.5 ten thousand, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the index of the fusion of product is 4.2g/10min.
Embodiment 14
70wt% hydroxy acid solution 6Kg is put in 10 liters of there-necked flasks, add benzoic acid stannous 12g (0.2wt%) again, with raise gradually dehydration temperaturre to 100 ℃ of 2h, the later stage is reduced the pressure of reaction system gradually.Continuation is warming up to 140 ℃ with 2h.Along with removing of aqueous solvent, the intermolecular dehydrating condensation of glycolic acid begins, and uses 4h, system temperature to rise to 180 ℃ at last again, and the molecular weight of oligomeric hydroxy acetate is 1500～8000.Glycolide is collected in 200～270 ℃ of cracking then, and 5h finishes, and thick product is 2.32Kg, and yield 72%, crude product fusing point are 92 ℃.With twice recrystallization of ethyl acetate, the recrystallization afterproduct is 1.72Kg, and productive rate is for accounting for thick product 74%, and ultimate yield is 54%, and the product fusing point is 92～93 ℃.
Embodiment 15
70wt% hydroxy acid solution 6Kg is put in 10 liters of there-necked flasks, add benzoic acid stannous 3g (0.05wt%) again, with raise gradually dehydration temperaturre to 100 ℃ of 2h, the later stage is reduced the pressure of reaction system gradually.Continuation is warming up to 140 ℃ with 2h.Along with removing of aqueous solvent, the intermolecular dehydrating condensation of glycolic acid begins, and uses 6h, system temperature to rise to 180 ℃ at last again, and the molecular weight of oligomeric hydroxy acetate is 1500～8000.Glycolide is collected in 200～270 ℃ of cracking then, and 6h finishes, and thick product is 2.23Kg, and yield 70%, crude product fusing point are 91 ℃.
Embodiment 16
70wt% hydroxy acid solution 6Kg is put in 10 liters of there-necked flasks, add benzoic acid stannous 60g (1wt%) again, with raise gradually dehydration temperaturre to 100 ℃ of 2h, the later stage is reduced the pressure of reaction system gradually, continues to be warming up to 140 ℃ with 2h.Along with removing of aqueous solvent, the intermolecular dehydrating condensation of glycolic acid begins, and uses 3h, system temperature to rise to 180 ℃ at last again, and the molecular weight of oligomeric hydroxy acetate is 1500～8000.Glycolide is collected in 200～270 ℃ of cracking then, and 4h finishes, and thick product is 2.28Kg, and yield 71%, crude product fusing point are 90 ℃.
Embodiment 17
The glycolide process ethyl acetate solvent recrystallization purification that obtains in the foregoing description is obtained the polymer grade glycolide, and fusing point is 92～93 ℃.
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 100g, benzoic acid stannous 0.05g (0.05wt%), join in the 200ml reaction bulb of vacuum drying, then, the beginning reaction temperature is controlled at 110～125 ℃ of stirrings and carries out bulk polymerization, and about 2～4 hours, the system viscosity increased, stop to stir, constantly heat release in the course of reaction, rising reaction temperature to 130 ℃ continues reaction 48 hours, because poly-glycolide can not be dissolved in the common solvent, to react the vial cooled with liquid nitrogen, the fried bottle of boiling water takes out co-glycolide polymers, adopt the liquid nitrogen frozen breaking method, preparation particle masterbatch, fusing point is 9.2g/10min at 220～225 ℃ 230 ℃ of following melt index.
Embodiment 18
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 100g, benzoic acid stannous 0.01g (0.01wt%), join in the 200ml reaction bulb of vacuum drying, then, the beginning reaction temperature is controlled at 110～125 ℃ of stirrings and carries out bulk polymerization, and about 4～6 hours, the system viscosity increased, stop to stir, constantly heat release in the course of reaction, rising reaction temperature to 130 ℃ continues reaction 72 hours, because poly-glycolide can not be dissolved in the common solvent, to react the vial cooled with liquid nitrogen, the fried bottle of boiling water takes out co-glycolide polymers, adopt the liquid nitrogen frozen breaking method, preparation particle masterbatch, fusing point is 5.1g/10min at 222～225 ℃ 230 ℃ of following melt index.
Embodiment 19
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 100g particle, benzoic acid stannous 0.1g (0.1wt%), join in the 200ml reaction bulb of vacuum drying, then, the beginning reaction temperature is controlled at 110～125 ℃ of stirrings and carries out bulk polymerization, and about 2～4 hours, the system viscosity increased, stop to stir, constantly heat release in the course of reaction, rising reaction temperature to 130 ℃ continues reaction 48 hours, because poly-glycolide can not be dissolved in the common solvent, to react the vial cooled with liquid nitrogen, the fried bottle of boiling water takes out co-glycolide polymers, adopt the liquid nitrogen frozen breaking method, preparation particle masterbatch, fusing point is 14.6g/10min at 220～224 ℃ 230 ℃ of following melt index.
Embodiment 20
Under the condition of anhydrous and oxygen-free, get refined 6-caprolactone 100g, benzoic acid stannous 0.025g (0.025wt%), join in the 200ml reaction bulb of vacuum drying, then, the beginning reaction temperature is controlled at 110～125 ℃ of stirrings and carries out bulk polymerization, about 4～6 hours, the system viscosity increases, stop to stir constantly heat release in the course of reaction, rising reaction temperature to 130 ℃, continue reaction 72 hours, polymer (PCL) is used precipitation with alcohol, after the drying again through the chloroform dissolving, the productive rate of polymer is 96%, measuring viscosity-average molecular weight is 80,000, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the melt index of product is 3.7g/10min.
Embodiment 21
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 20g, L-lactide 80g, benzoic acid stannous 0.03g (0.03wt%) joins in the 200ml reaction bulb of vacuum drying, then, the beginning reaction temperature is controlled at 110～125 ℃ of stirrings and carries out bulk polymerization, about 2～4 hours, the system viscosity increased, and stopped to stir, constantly heat release in the course of reaction, rising reaction temperature to 130 ℃ continues reaction 72 hours, will react the vial cooled with liquid nitrogen, the fried bottle of boiling water, take out glycolide-lactide copolymer, adopt the liquid nitrogen frozen breaking method, preparation particle masterbatch.Polymer dissolves through chloroform, uses precipitation with alcohol again, and after the drying, the productive rate of polymer is 95%, and inherent viscosity is 2.68, under 190 ℃, and capillary diameter 1.095mm, under the pressure of 2.16kg, the melt index of product is 7.7g/10min.
Embodiment 22
Operating procedure is with embodiment 21, substitute the L-lactide with the D-lactide, polymer dissolves through chloroform, uses precipitation with alcohol again, after the drying, the productive rate of polymer is 96%, inherent viscosity is 2.82, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the melt index of product is 7.3g/10min.
Embodiment 23
Operating procedure is with embodiment 21, use meso D, the L-lactide substitutes the L-lactide, and polymer dissolves through chloroform, use precipitation with alcohol again, after the drying, the productive rate of polymer is 94%, and inherent viscosity is 2.23, under 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the melt index of product is 8.3g/10min.
Embodiment 24
Operating procedure is with embodiment 21, use racemic D, the L-lactide substitutes the L-lactide, and polymer dissolves through chloroform, use precipitation with alcohol again, after the drying, the productive rate of polymer is 95%, and inherent viscosity is 3.42, under 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the melt index of product is 5.3g/10min.
Embodiment 25
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 20g, 6-caprolactone 80g, benzoic acid stannous 0.03g (0.03wt%) joins in the 200ml reaction bulb of vacuum drying, then, the beginning reaction temperature is controlled at 110～125 ℃ of stirrings and carries out bulk polymerization, about 4～6 hours, the system viscosity increased, and stopped to stir, constantly heat release in the course of reaction, rising reaction temperature to 130 ℃ continues reaction 72 hours, and polymer dissolves through chloroform, use precipitation with alcohol again, after the drying, the productive rate of polymer is 97%, and measuring inherent viscosity is 3.73, under 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the melt index of product is 4.9g/10min.
Embodiment 26
Under the condition of anhydrous and oxygen-free, get polymer grade L-lactide 50g, 6-caprolactone 50g, benzoic acid stannous 0.03g (0.03wt%) joins in the 200ml reaction bulb of vacuum drying, then, the beginning reaction temperature is controlled at 110～125 ℃ of stirrings and carries out bulk polymerization, about 4～6 hours, the system viscosity increased, and stopped to stir, constantly heat release in the course of reaction, rising reaction temperature to 130 ℃ continues reaction 72 hours, and polymer dissolves through chloroform, use precipitation with alcohol again, after the drying, the productive rate of polymer is 96%, and measuring inherent viscosity is 3.86, under 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the melt index of product is 4.6g/10min.
Embodiment 27
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 20g, polymer grade L-lactide 30g, 6-caprolactone 50g, benzoic acid stannous 0.03g (0.03wt%), join in the 200ml reaction bulb of vacuum drying, then, the beginning reaction temperature is controlled at 110～125 ℃ of stirrings and carries out bulk polymerization, about 4～6 hours, the system viscosity increases, stop to stir constantly heat release in the course of reaction, rising reaction temperature to 130 ℃, continue reaction 72 hours, polymer dissolves through chloroform, uses precipitation with alcohol again, after the drying, the productive rate of polymer is 96%, measuring inherent viscosity is 2.36, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the melt index of product is 7.7g/10min.
Embodiment 28
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 5g, polymer grade L-lactide 45g, benzoic acid stannous 0.015g (0.03wt%), xylene solvent 50ml joins in the 200ml reaction bulb of vacuum drying, carries out polymerisation in solution.The beginning reaction temperature is controlled at 120～125 ℃ of stirrings and carries out polymerisation, and about 4～6 hours, the system viscosity increased, stop to stir, rising reaction temperature to 130 ℃ continues reaction 72 hours, add the toluene solvant dissolving and take out polymer solution, use precipitation with alcohol again, after the drying, the productive rate of polymer is 94%, measuring inherent viscosity is 2.38, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the melt index of product is 8.2g/10min.
Embodiment 29
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 5g, 6-caprolactone 45g, benzoic acid stannous 0.015g (0.03wt%), xylene solvent 50ml joins in the 200ml reaction bulb of vacuum drying, carries out polymerisation in solution.The beginning reaction temperature is controlled at 120～125 ℃ of stirrings and carries out polymerisation, and about 4～6 hours, the system viscosity increased, stop to stir, rising reaction temperature to 130 ℃ continues reaction 72 hours, add the toluene solvant dissolving and take out polymer solution, use precipitation with alcohol again, after the drying, the productive rate of polymer is 96%, measuring inherent viscosity is 3.45, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the melt index of product is 5.3g/10min.
Embodiment 30
Under the condition of anhydrous and oxygen-free, get polymer grade L-lactide 25g, 6-caprolactone 25g, benzoic acid stannous 0.015g (0.03wt%), xylene solvent 50ml joins in the 200ml reaction bulb of vacuum drying, carries out polymerisation in solution.The beginning reaction temperature is controlled at 120～125 ℃ of stirrings and carries out polymerisation, and about 4～6 hours, the system viscosity increased, stop to stir, rising reaction temperature to 130 ℃ continues reaction 72 hours, add the toluene solvant dissolving and take out polymer solution, use precipitation with alcohol again, after the drying, the productive rate of polymer is 96%, measuring inherent viscosity is 2.26, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the melt index of product is 8.3g/10min.
Embodiment 31
Under the condition of anhydrous and oxygen-free, get polymer grade glycolide 10g, polymer grade L-lactide 15g, 6-caprolactone 25g, benzoic acid stannous 0.015g (0.03wt%), xylene solvent 50ml join in the 200ml reaction bulb of vacuum drying, and the tube sealing of finding time carries out polymerisation in solution.The beginning reaction temperature is controlled at 120～125 ℃ of stirrings and carries out polymerisation, and about 4～6 hours, the system viscosity increased, stop to stir, rising reaction temperature to 130 ℃ continues reaction 72 hours, add the toluene solvant dissolving and take out polymer solution, use precipitation with alcohol again, after the drying, the productive rate of polymer is 96%, measuring inherent viscosity is 2.48, under 190 ℃, and capillary diameter 1.095mm, 2.16kg pressure under, the melt index of product is 9.6g/10min.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technical staff of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some instantiations as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (10)
1, the benzoic acid stannous purposes that forms the catalyst of lact-acid oligomer as acid by dehydrating lactic.
2, benzoic acid stannous purposes as catalyst according to claim 1 is characterized in that, described lactic acid is L-lactic acid, D-lactic acid, D, one or more mixing in the L-lactic acid.
3, the benzoic acid stannous purposes that generates the catalyst of lactide as the lact-acid oligomer cracking.
4, the benzoic acid stannous purposes that becomes the catalyst of PLA as lactide homopolymerization symphysis.
According to claim 3 or 4 described purposes, it is characterized in that 5, described lactide is the L-lactide, D-lactide, meso D, one or more mixing in the L-lactide; Wherein said equal polymerization method is a kind of in polymerisation in bulk or the polymerisation in solution.
6, the benzoic acid stannous purposes that generates the catalyst of oligomeric hydroxy acetate as glycolic acid dehydration.
7, the benzoic acid stannous purposes that generates the catalyst of glycolide as the cracking of oligomeric hydroxy acetate.
8, benzoic acid stannously become the purposes of the catalyst of poly-glycolide, describedly all be polymerized to a kind of in polymerisation in bulk or the polymerisation in solution as glycolide homopolymerization symphysis.
9, the purposes of benzoic acid stannous catalyst as the combined polymerization between glycolide, lactide, 6-caprolactone both or the three.
10, purposes according to claim 9 is characterized in that, described lactide is the L-lactide, D-lactide, D, one or more mixing in the L-lactide; Wherein said process for copolymerization is a kind of in polymerisation in bulk or the polymerisation in solution.
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| CN2008101819965A Division CN101492441B (en) | 2006-01-27 | 2006-01-27 | Uses of benzoic acid stannous as catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101463124B (en) * | 2007-12-21 | 2011-08-17 | 东丽纤维研究所（中国）有限公司 | Method for preparing polylactic acid with metal sulphonate as catalyst |
| CN104803844A (en) * | 2015-03-27 | 2015-07-29 | 中国科学院长春应用化学研究所 | Method for preparing lactate from waste containing polylactic acid chain segments |
| CN104892564A (en) * | 2015-06-04 | 2015-09-09 | 中国科学院长春应用化学研究所 | Method for preparing lactide from high molecular weight polylactic acid |
| CN105418900A (en) * | 2016-01-12 | 2016-03-23 | 中国科学院长春应用化学研究所 | Preparation methods of butylene succinate and polylactic acid segmented copolymer |
| CN105524262A (en) * | 2016-01-12 | 2016-04-27 | 中国科学院长春应用化学研究所 | Preparation methods for poly(polybutylene glycol-adipate-terephthalate) and polylactic-acid block copolymer of poly(polybutylene glycol-adipate-terephthalate) |
| CN109280158A (en) * | 2018-04-05 | 2019-01-29 | 河南金丹乳酸科技股份有限公司 | The method for producing poly- D-ALPHA-Hydroxypropionic acid using D- lactide ring-opening polymerisation |
| CN110078634A (en) * | 2019-05-23 | 2019-08-02 | 大连汇鹏达化工有限公司 | A kind of preparation method and application of amino acid stannous complex |
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| US3792010A (en) * | 1972-03-27 | 1974-02-12 | Ethicon Inc | Plasticized polyester sutures |
| US5317064A (en) * | 1992-12-11 | 1994-05-31 | E. I. Du Pont De Nemours And Company | Manufacture of polylactide stereocomplexes |
| CN1098882C (en) * | 1998-06-03 | 2003-01-15 | 中国科学院化学研究所 | Biodegradable high polymer and its preparation method |
| CN1133680C (en) * | 1999-04-26 | 2004-01-07 | 中国科学院化学研究所 | Biodegradable three-element copolymerized ester and its processing process |
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