CN101054371A - Preparation method for glycolide - Google Patents
Preparation method for glycolide Download PDFInfo
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- CN101054371A CN101054371A CN 200710041157 CN200710041157A CN101054371A CN 101054371 A CN101054371 A CN 101054371A CN 200710041157 CN200710041157 CN 200710041157 CN 200710041157 A CN200710041157 A CN 200710041157A CN 101054371 A CN101054371 A CN 101054371A
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Abstract
The present invention belongs to the technology field for preparing cyclocompound, specific as preparation method of glycolide. The method synthesizes high purity and high productivity glycolide crystal with high-purity glycolic acid crystal as raw material through a series of steps including dewatering polycondensation, melting polycondensation, depolymerization reaction and recrystallization purifying etc. The present invention prepares glycolide through depolymerizing polyglycolic acid oligomer which is prepared by polycondensating glycolic acid in presence of coexistent two catalysts, and purify primary product of glycolide through controlling recrystallization of glycolide by dropping low boiling point solvent at appropriate temperature.The method guarantee the high conversion rate of polyglycolic acid oligomer in depolymerization procedure and stability of crystal formation of glycolide in procedure of recrystallization, and can increase productivity of glycolide.
Description
Technical field
The invention belongs to the ring compound preparing technical field, be specifically related to a kind of preparation method of glycollide.
Background technology
Polyglycolic acid is a kind of aliphatic polyester with excellent biodegradable and biocompatibility, is widely used in damaged reparation, the repairing of tendon and the aspects such as stitching of human body or animal blood vessels, muscle and other tissue of internal fixing, bone of human body or animal bone fracture.At present, the method for synthetic polyglycolic acid mainly contains direct polymerization method and glycollide ring-opening polymerization method.The reaction formula of direct polymerization method is as follows:
Adopt the oxyacetic acid polycondensation of directly dewatering, generally can only obtain relative molecular weight, be difficult to satisfy the use properties of material at tens to several thousand oligopolymer.And the cyclic dimer glycollide ring-opening polymerization of adopting oxyacetic acid can the synthetic macromolecule amount polyglycolic acid, the polyglycolic acid oligopolymer that relative molecular weight is lower is then commonly used does the initial reactant that the high temperature depolymerization prepares glycolide monomer, its reaction formula is as follows:
In the ring-opening polymerization of glycollide,, must use highly purified glycolide monomer in order to obtain the high-molecular weight polyglycolic acid.The preparation of glycollide is generally undertaken by two steps, at first is to generate the relatively short glycolic acid oligomers of molecular chain, generates the ring-type glycollide then under reduced pressure.Usually, the productive rate that the method by this polymerization-depolymerization prepares cyclic ester is lower, up to now, has adopted the whole bag of tricks to improve monomeric productive rate of these cyclic esters and purity.
US5091544, US5023349, US5117008, US5266706 etc. disclose by adopt feeding inert gas to be increased reaction interface and impels oligopolymer rapidly to the conversion of cyclic monomer, and adopts water-fast non-polar solvent to reclaim cyclic monomer from air-flow.But because the generating rate of cyclic dimer is slower, this method still is difficult to reduce production costs.US4727163 discloses the method that adopts the copolymer cyclic ester of heating oxyacetic acid and high temperature resistant polyethers, though high temperature resistant polyethers can be reused by repeatedly adding the oxyacetic acid copolymerization, but need expend a large amount of polynary polyethers, at high temperature polymkeric substance has a lot of side reactions generations simultaneously, the for example charing of isomer, superpolymer etc. causes reactor to be difficult to cleaning.
US5830991 adopt to add the high boiling point polar organic solvent in the polyglycolic acid oligopolymer to reduce reaction system viscosity and depolymerization temperature of reaction, US6891048B2, US691639B2, CN1496359A, CN1501923A etc. also mention polyglycolic acid oligopolymer and polar organic solvent add the depolymerization system simultaneously and introduce simultaneously divalence or polyvalent cation form vitriol and or the organic acid salt stablizer prevent the generation of side reaction, but caused the thick product of glycollide to be difficult to purifying because of being mixed with this kind solvent.
Above-mentioned patent has also been mentioned the catalyzer that is adopted in this technological process.Be often used as transesterify or polycondensation catalyst as the amphoteric metal oxide compound of mentioning among the CN1488628 such as zinc oxide, weisspiessglanz, stannic oxide, plumbous oxide etc.US5374743 then illustrate the polyglycolic acid oligopolymer high temperature separate in the collecting process introduce depolymerization catalyzer such as rare earth compounds such as tin or tin compound, yttrium, antimony compounds etc. can be with the molecular weight control of residual reactants 1.2 times at feed ratio in.
That adopts in the purifying process of cyclic ester at present, has solution crystal process, solvent absorption, solvent extraction process, distillation method, fusion-crystallization method and a subliming method etc.Though these methods can be crossed the purifying that obtains cyclic ester in the laboratory, high energy consumption, equipment and solvent expense make them be difficult to reach business-like scale, have also limited their application.US5686630, US5856523, CN1058210A etc. make crude product be divided into two-phase by introduce water-soluble solvent in product, the organic solvent that promptly contains cyclic ester mutually and the water-soluble solvent of absorption impurity mutually, reach the purpose of separation and purification cyclic ester thus.Employings such as US5274073, US6277951, AU2003295252 are separated as the air-flow component cyclic ester of rac-Lactide or glycollide or mixture with impurity, these separation method process complexity, and yield is not high.
Employing hydrolysis method such as CN1112559, JP10025288, US5502215 prepare the Study of Meso-Lactide hydrolysis rac-Lactide of high-optical-purity, but after the hydrolysis treatment, still need recrystallization to be further purified.Recrystallization method is few because of its operation steps, technology comparatively ripe use comparatively extensive.CN1488628, FR2843390, WO9315069 etc. introduce recrystallization method purifying rac-Lactide.But the research for recrystallization method purifying rac-Lactide mostly is choice of Solvent greatly at present, as patent US4727163, CN1583740, CN1757643A etc. adopt ethyl acetate, JP10279577 adopts the lower member ester class, US6313319, CN1757644A etc. use alcohols, JP6279435 uses lower alcohol, ketone, ester class or its mixture etc., though these patents disclose the recrystallizing technology of the rac-Lactide in the different solvents, but for glycollide, because it has chemical property different with rac-Lactide and dissolving power, and its easier hydrolysis or alcoholysis still are worth exploring for its recrystallizing technology Study on Conditions.
Summary of the invention
The objective of the invention is to propose the production method of the high ring compound glycollide of a kind of productive rate.
The present invention proposes by oxyacetic acid dehydration polycondensation and the high-temperature fusion polycondensation prepares the polyglycolic acid oligopolymer and depolymerization prepares in the process of glycollide, introduce high-temperature fusion polycondensation and two kinds of catalyzer, make two kinds of catalyzer be present in the depolymerization reaction system jointly, impel of the conversion of polyglycolic acid oligopolymer, thereby improved the productive rate of glycollide to glycollide.
The invention allows for and adopt mixed solvent heating for dissolving glycollide, and the method that drips low boiling point solvents such as methyl alcohol, ether, methylene dichloride, Skellysolve A, tetrahydrofuran (THF) under certain temperature range is impelled the rapid formation of glycollide nucleus, thereby shorten by the required time of nucleation in the slow temperature-fall period, and can stably obtain laminar glycollide crystal.
With the oxyacetic acid is raw material, and the synthesis technique of glycollide comprises polycondensation and two parts of depolymerization.Among the present invention, adopting highly purified oxyacetic acid crystal is raw material, by the synthetic purity height of series of steps such as dehydration polycondensation, melt phase polycondensation, depolymerization reaction, recrystallization purifying, glycollide crystal that productive rate is high.Its concrete steps are as follows:
(1) dehydration polycondensation, in the presence of condensation catalysts such as the metal of IV, V, VII main group and IIB subgroup or metallic compound or transesterification catalyst, with purity is that 99.5% oxyacetic acid crystal is warming up to 160-180 ℃ from 80 ℃ under reduced pressure, carry out condensation reaction or transesterification reaction, till not having low molecular weight substance (as water) substantially and being distilled out, obtain white polyglycolic acid oligopolymer;
(2) melt phase polycondensation, the halogenide or the organic acid compound that in the oligopolymer that step (1) generates, add tin, perhaps rare earth metal complex, perhaps zinc halogenide or organic zinc compound, perhaps catalyzer such as iron halide or organoiron compound, elevated temperature continues polycondensation 2-10 hour to 200-240 ℃ under the vacuum condition of 1KPa-5KPa simultaneously, makes the complete fusion of polyglycolic acid oligopolymer that has cured;
(3) depolymerization reaction, treat the complete fusion of polyglycolic acid oligopolymer after, further improve temperature of reaction to 230-280 ℃, simultaneously gas clean-up makes polyglycolic acid oligopolymer generation depolymerization reaction to 10-300Pa, underpressure distillation goes out the glycollide crude product;
(4) recrystallization purifying, the glycollide crude product is slightly yellow because of containing acidic impurities, must carry out purification process.The glycollide crude product is being lower than under 70 ℃ the condition, heating for dissolving is in the mixed solvent by lower member ester class or lower alcohols and two kinds of solvent compositions of rudimentary ketone, be cooled to then between 45-60 ℃, in the low boiling point solvents such as interpolation methyl alcohol, ether, methylene dichloride, Skellysolve A or tetrahydrofuran (THF) one or several, impel the formation of glycollide nucleus in the supersaturated solution of clear, slowly be cooled to the frozen water temperature then, promptly obtain the glycollide product of purifying.
The glycollide of the present invention's preparation is determined its chemical constitution and purity thereof by nucleus magnetic resonance (Nuclear magnetic resonance).
The present invention prepares glycollide by polyglycolic acid oligopolymer depolymerization under the condition of two kinds of catalyzer coexistences that the oxyacetic acid polycondensation generates, by dripping low boiling point solvent control glycollide recrystallization in suitable temperature to glycollide head product purifying, this method guarantees high conversion and glycollide the stability that in recrystallization process crystal generate of polyglycolic acid oligopolymer in separating collecting process, can improve the productive rate of glycollide.
Below each step is described further.
1, the polycondensation of oxyacetic acid
As an example but do not limit, oxyacetic acid is mainly by polycondensation dehydration preparation polyglycolic acid oligopolymer.Adopt commercially available oxyacetic acid solution, glycolic acid esters or hydroxyl acetate all can prepare the polyglycolic acid oligopolymer, but because residual metal ion is arranged in these raw materials, as alkalimetal ion, be brought into the depolymerization reaction system at the glycolic acid oligomers that is used for depolymerization reaction, thereby cause depolymerization reaction system instability.Because the influence of the metal ion that raw material is introduced, it is oxyacetic acid crystal 99.5% or more that the present invention adopts purity in order to reduce, and this highly purified oxyacetic acid can pass through purification process acquisitions such as recrystallization, distillation.
Synthesis of hydroxy acetate oligopolymer can join condensation catalysts such as the metal of IV, V, VII main group and IIB subgroup or metallic compound or transesterification catalyst in 99.5% the oxyacetic acid crystal, after 80 ℃ of fusions, progressively be warming up to 160 ℃-180 ℃, under the condition of decompression, carry out condensation reaction or transesterification reaction, till constantly dehydration extremely can not steam, get the white solid thing and be the polyglycolic acid oligopolymer.
This polyglycolic acid oligopolymer can be directly used in depolymerization reaction, if with the polyglycolic acid oligopolymer of non-solvent such as benzene or toluene wash gained, and then can be with unreacted or low molecular weight substance from wherein removing.If do not adopt the method for this washing, tin halide that the high-temperature fusion polycondensation phase can be added or organic acid compound or rare earth metal complex or zinc halogenide or organic zinc compound or catalyzer such as iron halide or organoiron compound add with polycondensation catalyst or transesterification catalyst together in this reaction beginning, because the continuity of reaction, these two kinds of catalyzer can coexist as high-temperature fusion polycondensation stage and depolymerization step of reaction.Also just be based on the consideration of glycollide productive rate, introducing the high-temperature fusion polycondensation.
2. high-temperature fusion polycondensation
The high-temperature fusion polycondensation is meant that low-molecular-weight polyglycolic acid oligopolymer continues the process of reaction under the high-temperature fusion condition.Usually, the polyglycolic acid oligopolymer by oxyacetic acid polycondensation preparation can directly be used for carrying out depolymerization and prepares glycollide.But because experimental study learns that the molecular weight of polyglycolic acid oligopolymer has very material impact to the reaction of preparation glycollide.If molecular weight is low excessively, depolymerize to the ring difficulty, cause the glycollide productive rate not high; If molecular weight is too high, will cause viscosity to rise, polymkeric substance is difficult to handle, and should make high molecular weight polymers hydrolysis recovery again.Patent US5053522 points out the molecular weight of polyglycolic acid oligopolymer at 400-2000, preferred 500-800.The fusing point of the above-mentioned polyglycolic acid oligopolymer that obtains should be at 180 ℃ or higher, are to adopt dsc (DSC) to measure under nitrogen atmosphere with 10 ℃/minute temperature rise rate.
The high-temperature fusion polycondensation that the present invention adopts is halogenide or organic acid compound or rare earth metal complex or zinc halogenide and organic zinc compound or the catalyzer such as iron halide and organoiron compound that add tin in by the oligopolymer of oxyacetic acid polycondensation preparation, elevated temperature is to 200-240 ℃ simultaneously, under the vacuum condition of 1KPa-5KPa, continue reaction for some time, make the complete fusion of polyglycolic acid oligopolymer that has cured, make the molecular weight of polyglycolic acid oligopolymer and molecular weight distribution controlled simultaneously.Elevated temperature should be chosen as 200-240 ℃ to more than the glycolic acid oligomers fusing point, is preferably 210-220 ℃.The control of vacuum tightness should be unlikely to glycollide and steam in this step of reaction, simultaneously can not be low excessively, otherwise polycondensation phase unreacted or low molecular weight substance and side reaction product are not easy to migrate to gas phase mutually and be pulled away from the oligopolymer fusion.Through the pH pH-value determination pH, these by products mainly are that pH is the acidic substance of 2-3, and it is present in the raising that is unfavorable for the glycollide productive rate in the depolymerization system.Therefore, the vacuum tightness of high-temperature fusion polycondensation phase can be chosen as 1KPa-5KPa, is preferably 1-3KPa.
Following table 1 has been listed the influence of the use of high-temperature fusion condensation temperature, reaction times and two kinds of catalyzer to the glycollide productive rate, prolonging the high-temperature fusion polycondensation reaction time can make the molecular weight of polyglycolic acid oligopolymer further improve under molten state, and make molecular weight distribution homogeneous more by transesterification reaction, the productive rate of glycollide obviously improves under the common condition that exists of two kinds of catalyzer, but the prolongation melt polycondensation reaction time also can be caused the rising of the energy and cost.For the high-temperature fusion polycondensation, its reaction times can be chosen as 2-10h, is preferably 4-8h.
Table 1. melt phase polycondensation temperature, reaction times and catalyzer are to the influence of glycollide productive rate
| Numbering | Temperature of reaction (℃) | Reaction times (h) | Catalyzer | Productive rate (%) |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 | 210-220 210-220 210-220 210-220 | 4 10 3 8 | I I I+II I+II | 61 84 79 86 |
Annotate: catalyst I and II represent first kind and second kind of catalyzer respectively, and productive rate is the per-cent of actual output and theoretical yield.
3. depolymerization reaction
The depolymerization method of polyglycolic acid oligopolymer comprises fusing depolymerization, solution depolymerization and solid phase depolymerization.The present invention adopts the fusing depolymerization, and its process is that heating polyglycolic acid oligopolymer is to the depolymerization temperature under decompression or normal pressure, and glycollide distills from the depolymerization system, reclaims glycollide from distillate.The polyglycolic acid oligopolymer is the reactant of depolymerization system, can be to make by oxyacetic acid dehydration polycondensation, and also can be product by high molecular polyglycolic acid degraded gained.The present invention considers the productive rate of glycollide, introduce the high-temperature fusion polycondensation, the depolymerization reaction thing is the product of the above-mentioned melt polycondensation reaction of process after for some time, it has the higher molecular weight and the molecular weight distribution of homogeneous more with respect to the polyglycolic acid oligopolymer that is generated by the first step polycondensation stage, and by product still less is present in the depolymerization reaction system.The polyglycolic acid oligopolymer that polycondensation obtains through high-temperature fusion can carry out the fusion depolymerization reaction continuously directly as reactant; But also cooling curing is as the dry distillation reactor thing of solid phase depolymerization.Compare the dry distillation of solid phase depolymerization, the polyglycolic acid oligopolymer of maintenance molten state more helps the formation and the travelling speed of glycollide.So the present invention is preferably the molten state polyglycolic acid oligopolymer of continuous depolymerization after the high-temperature fusion polycondensation.
Heating is carried out under decompression or normal pressure.Under normal pressure, should use inert atmosphere or adopt the mode of inert gas to take glycollide out of, the rare gas element that adopts is a nitrogen usually.For under reduced pressure, should adopt the vacuum tightness of 10-1KPa, be preferably 10-300Pa.Be at least 230 ℃ for the temperature that is heated to polyglycolic acid oligopolymer generation depolymerization reaction, usually, this oligopolymer be heated to 230-280 ℃, be preferably 230-260 ℃.
Along with glycollide distills from the depolymerization reaction system, the volume of depolymerization reaction system descends, and the molecular weight of polyglycolic acid oligopolymer also descends, and the formation speed of glycollide descends.If further improve the depolymerization reaction temperature then can impel the generation of glycollide, perhaps in reactive system, add the minimizing that a certain amount of new glycolic acid oligomers then can remedy reactant, depolymerization reaction is carried out continuously or repeatedly, thereby improve productive rate and cutting down cost.
4. catalyzer
Preparing in the process of glycollide by oxyacetic acid polycondensation dehydration preparation polyglycolic acid oligopolymer with by the depolymerization of polyglycolic acid oligopolymer, mention the use of catalyzer in existing many documents and the patent, wherein polycondensation catalyst or transesterification catalyst are often used as in the dehydration polycondensation of oxyacetic acid, this class catalyzer generally adopts amphoteric metal powder or its oxide compound etc., as zinc powder, glass putty, zinc oxide, weisspiessglanz, stannic oxide and plumbous oxide etc.For two kinds of catalyzer mentioning among the present invention, preceding a kind of catalyzer is polycondensation or transesterification catalyst, can help oxyacetic acid dehydration polycondensation and become the polyglycolic acid oligopolymer.This catalyzer is generally the metal or the metallic compound of IV in the periodic table of elements, V, VII main group and IIB subgroup, with IV main group, V main group or IIB subgroup metal for well, the former is metal-powder, oxide compound, halogenide or the carboxylate salt of tin or zinc particularly, the latter is generally oxide compound, as antimonous oxide etc.This class catalyzer should add when the oxyacetic acid polycondensation begins, and the mass percent of its adding is the 0.1-6% of oxyacetic acid charging capacity, is preferably 0.3-1%.
Dissolve the another kind of catalyzer that polycondensation is used, be generally the catalyzer that the ring-opening polymerization of ring-type monoesters prepares high molecular weight polyesters, this kind catalyzer helps increasing the molecular weight of oligopolymer, also helps the generation of depolymerization reaction simultaneously when high temperature.This catalyzer is generally the halogenide or the organic acid compound of tin, rare earth metal complex, zinc halogenide or organic zinc compound, iron halide or organoiron compound etc., as tin protochloride, stannous octoate, the inferior tin of lactic acid, methyl ethyl diketone zirconium, zinc lactate, zinc chloride, iron trichloride, iron lactate or ferric acetyl acetonade, or wherein any two or more mixture etc., be preferably the stannous salt, particularly stannous octoate of carboxylic acid.Patent US5374743 mentions by the amount that increases catalyzer can quicken the generating rate of glycollide or the relative hydrolysis of rac-Lactide, and mentions the 1-8% of the mass percent of this catalyzer in the oligopolymer charging capacity, is preferably 2-6%.In the high-temperature fusion polycondensation phase, because first kind of polycondensation or transesterification catalyst still are present in the reaction system, the amount of the another kind of catalyzer of employing is difficult for too much for the present invention, and the high-temperature fusion elementary reaction is violent, system is unstable otherwise cause easily.This catalyzer should add when the high-temperature fusion polycondensation begins; If the employing continuous production processes then also can add with polycondensation catalyst or transesterification catalyst together, the mass percent of adding should be controlled at below 1% of oxyacetic acid charging capacity, is preferably 0.3-0.7%.
5. the purifying of glycollide
Prepare in the process of glycollide in the depolymerization of polyglycolic acid oligopolymer high temperature, often be accompanied by the reaction of some high temperature secondary, cause the glycollide crude product that distills out slightly faint yellow because of containing impurity.Here adopt the method purifying glycollide of recrystallization, the glycollide crude product is being lower than under 70 ℃ the condition, heating for dissolving forms clear solution in the mixed solvent of being made of lower member ester class, alcohols or ketone, be cooled to then between 45-60 ℃ and form supersaturated solution, in the low boiling point solvents such as interpolation methyl alcohol, ether, methylene dichloride, Skellysolve A, tetrahydrofuran (THF) one or several add simultaneously, impel the formation of glycollide nucleus, then with the rate of temperature fall of 5-10 ℃/h to the frozen water temperature.
The mixed solvent that uses in the recrystallization process requires a kind of solvent big to the solubleness of glycollide, and as lower member ester class, lower alcohols, another kind of solvent is little and big to the solubleness of impurity to the solubleness of glycollide, as rudimentary ketone.Alternative mixed solvent is methyl acetate and acetone, methyl acetate and butanone, ethyl acetate and acetone, ethyl acetate and butanone, methyl alcohol and acetone, methyl alcohol and butanone, ethanol and acetone or alcohol and butanone etc., is preferably methyl acetate and acetone, ethyl acetate and acetone.Two kinds of solvent volume ratios are 3: 1 to 9: 1, and concrete ratio generally can be selected by the content of impurity in the glycollide, and for the recrystallization first time, because foreign matter content is more in the glycollide crude product, the volume ratio of two kinds of solvents can be greatly, as be 3: 1.For recrystallization for the second time or for the third time, because foreign matter content is less in the glycollide, can reduce the adding of ketones solvent, the volume ratio of two kinds of solvents can be smaller, as select 6 for use: 1--9: 1.Add-on as for mixed solvent can be determined according to the solubility curve of glycollide in this mixed solvent.Fig. 1 is the solubility curve of glycollide in ethyl acetate and acetone mixed solvent (3/1).Particularly, for the ethyl acetate and the acetone mixed solvent of volume ratio 3/1, be lower than 70 ℃ and guarantee that the volume add-on of mixed solvent can be chosen to be 1.1-1.5ml/g corresponding to the ratio of glycollide quality under the excessive slightly situation of solvent in Heating temperature.
Usually, can effectively faint yellow impurity in the glycollide be removed, also can remove foreign pigment in the glycollide crude product by in mixed solvent, adding methods such as activated carbon adsorption, heat filtering by the recrystallization method of mixed solvent.It is noted that simultaneously, glycollide is in esters solvent heating for dissolving process, though along with the rising solubleness of temperature is increasing, but the too high meeting of temperature causes ethyl acetate or glycollide hydrolysis, cause the loss that unknown compound or product occur, this unknown compound shows as impurity peaks in nucleus magnetic hydrogen spectrum, thereby influences the purity of glycollide.Therefore, the heating for dissolving temperature of glycollide should not surpass 70 ℃, is preferably between 60-65 ℃.
Usually, adopt the mode that reduces temperature to form supersaturated solution.In being lower than the temperature range of supersaturation point, the necessary first nucleation of glycollide can crystal growth.Nucleation mode is according to the difference of crystallization condition and difference, under cooling condition rapidly easily because heterogeneous nucleations such as impurity, wall are accounting for many fine crystals that form, under slow cooling condition since homogeneous nucleation and easy formation than macrocrystal.The present invention drips low boiling point solvent to this supersaturated solution in the temperature range of supersaturation point, the required time of nucleation is shortened in the formation of induced nuclei rapidly, avoids simultaneously helping growing into bigger laminar crystal owing to slowly lower the temperature.The boiling point of this solvent should be lower than the temperature range of supersaturation point, they volatilize easily and can be miscible in mixed solvent, concrete as methyl alcohol, ether, methylene dichloride, Skellysolve A, tetrahydrofuran (THF) etc., be first-selection wherein, also can adopt two kinds or two or more solvents to add simultaneously with the minimum ether of boiling point.The supersaturation point temperature range of this mixing solutions is 45-60 ℃, is preferably 50-55 ℃.The add-on of low boiling point solvent does not limit, and with till can forming the glycollide nucleus, is good with the amount that adds 0.1-3ml generally, is preferably 0.1-1ml.
Description of drawings
Fig. 1. the solubility curve of glycollide in ethyl acetate/acetone (3/1) mixed solvent.
Embodiment
Solubility curve
For measuring the solubility curve of glycollide in mixed solvent, preparation ethyl acetate/acetone (V/V:3/1) mixed solvent 40ml, pour in the there-necked flask, after being installed, whipping appts, reflux condensing tube and thermometer be put in the Water Tank with Temp.-controlled, control different bath temperatures, add the glycollide crystal gradually, be stirred to can not dissolve again till, calculate glycollide dissolved gram number under the differing temps, as shown in table 2 below.
Table 2. glycollide is dissolved in the gram number in the mixed solvent under differing temps
| Temperature (℃) | 25 | 40 | 50 | 55 | 60 | 65 | 68 |
| Gram number (g) | 6.4 | 8.5 | 14 | 18.6 | 25.8 | 35.5 | 42.5 |
Curve plotting is seen shown in Figure 1 in the summary of the invention.
Embodiment 1
In the single neck flask of 500ml, add 553.1g 99.5% oxyacetic acid crystal and 1.66g catalyst S b
2O
3, place oil bath pan, temperature rises to 90 ℃ from room temperature, treat dissolving fully after, beginning slowly vacuumizes, and constantly has liquid to steam, and solidifies to reactant with the temperature rise rate of 5-10 ℃/h to be creamy white, and till absence of liquid steams.Improve temperature again and continue to react 4 hours to 210-220 ℃, this process vacuum degree control is at 1-3KPa, and single port accepts to collect altogether in the flask 119ml weak yellow liquid.Use air set pipe instead subsequently and there-necked flask is accepted product, temperature of reaction rises to 260 ℃ gradually from 220 ℃, vacuum tightness also is increased between the 10-300Pa, constantly there is faint yellow glycollide crude product to steam, stopped reaction when not having glycollide and steam, get glycollide crude product 259.2g, productive rate is 61%.The glycollide crude product is put into single neck flask, pour the 214ml ethyl acetate into, elevated temperature and stirring and dissolving constantly drip 71ml acetone simultaneously, and the glycollide dissolution of crystals is complete during to 65 ℃ of left and right sides, is the achromaticity and clarification clear solution.Be cooled to 50-55 ℃ then and form the glycollide supersaturated solution, splashing into several is the 0.1-1ml ether, has a spot of crystal in liquid level or the solution and separates out, and slowly is cooled to the frozen water temperature then, forms the laminar crystal of a large amount of glycollide.Filtration washing final vacuum drying gets the about 130g of glycollide.
Embodiment 2
The oxyacetic acid crystal and the 2.829g catalyst S b that in the single neck flask of 500ml, add 470.7g 99.5%
2O
3, experimental installation after this is identical with embodiment 1 with condition, and prolonging the reaction times 210-220 ℃ high-temperature fusion polycondensation phase is 10h, and experimental installation thereafter is also identical with embodiment 1 with condition, and the glycollide crude product is 300.2g, productive rate is 84%.The glycollide crude product is put into single neck flask, pour the 270ml ethyl acetate into, elevated temperature and stirring and dissolving constantly drip 90ml acetone simultaneously, and the glycollide dissolution of crystals is complete during to 65 ℃, is the achromaticity and clarification clear solution.Be cooled to 50-55 ℃ then and form the glycollide supersaturated solution, splashing into several is the 0.1-1ml ether, has a spot of crystal in liquid level or the solution and separates out, and slowly is cooled to the frozen water temperature then, forms the laminar crystal of a large amount of glycollide.Filtration washing final vacuum drying gets the about 240g of glycollide.
Embodiment 3
In the single neck flask of 500ml, add 333.1g 99.5% oxyacetic acid crystal and 2.0g catalyst S b
2O
3, place oil bath pan, temperature rises to 90 ℃ from room temperature, treat dissolving fully after, beginning slowly vacuumizes, and constantly has liquid to steam, and solidifies to reactant with the temperature rise rate of 5-10 ℃/h to be creamy white, and till absence of liquid steams.Add the 3.331g stannous octoate catalyst in reaction system, improve temperature again and continue to react 3 hours to 210-220 ℃, this process vacuum degree control is at 1-3KPa.Use air set pipe instead subsequently and there-necked flask is accepted product, temperature of reaction rises to 260 ℃ gradually from 220 ℃, vacuum tightness also is increased between the 10-300Pa, constantly there is faint yellow glycollide crude product to steam, stopped reaction when not having glycollide and steam, get glycollide crude product 200.3g, productive rate is 79%.The glycollide crude product is put into single neck flask, pour the 195ml ethyl acetate into, elevated temperature and stirring and dissolving constantly drip 65ml acetone simultaneously, and the glycollide dissolution of crystals is complete during to 60 ℃ of left and right sides, is the achromaticity and clarification clear solution.Be cooled to 50-55 ℃ then and form the glycollide supersaturated solution, splashing into several is the 0.1-1ml ether, has a spot of crystal in liquid level or the solution and separates out, and slowly is cooled to the frozen water temperature then, forms the laminar crystal of a large amount of glycollide.Filtration washing final vacuum drying gets the about 155g of glycollide.
Embodiment 4
The oxyacetic acid crystal and the 1.458g catalyst S b that in the single neck flask of 500ml, add 243.0g 99.5%
2O
3After this experimental installation is identical with embodiment 3 with condition, after in reaction system, adding the 0.729g stannous octoate catalyst, 210-220 ℃ high-temperature fusion polycondensation reaction time is extended for 8h, thereafter experimental installation is also identical with embodiment 3 with condition, the glycollide crude product is 159.2g, and productive rate is 86%.The glycollide crude product is put into single neck flask, pour the 167ml ethyl acetate into, elevated temperature and stirring and dissolving, simultaneously continuous Dropwise 5 6ml acetone, the glycollide dissolution of crystals is complete during to 60 ℃, is the achromaticity and clarification clear solution.Be cooled to 50-55 ℃ then and form the glycollide supersaturated solution, splashing into several is the 0.1-1ml ether, has a spot of crystal in liquid level or the solution and separates out, and slowly is cooled to the frozen water temperature then, forms the laminar crystal of a large amount of glycollide.Filtration washing final vacuum drying gets the about 127g of glycollide.
Claims (6)
1, a kind of preparation method of glycollide is characterized in that concrete steps are as follows:
(1) dehydration polycondensation, in the presence of condensation catalysts such as the metal of IV, V, VII main group and IIB subgroup or metallic compound or transesterification catalyst, with purity is that 99.5% oxyacetic acid crystal is warming up to 160-180 ℃ from 80 ℃ under reduced pressure, carry out condensation reaction or transesterification reaction, till not having low molecular weight substance substantially and being distilled out, obtain white polyglycolic acid oligopolymer;
(2) melt phase polycondensation, the halogenide or the organic acid compound that in the oligopolymer that step (1) generates, add tin, perhaps rare earth metal complex, perhaps zinc halogenide or organic zinc compound, perhaps iron halide or organoiron compound catalyzer, elevated temperature continues polycondensation 2-10 hour to 200-240 ℃ under the vacuum condition of 1KPa-5KPa simultaneously, makes the complete fusion of polyglycolic acid oligopolymer that has cured;
(3) depolymerization reaction, treat the complete fusion of polyglycolic acid oligopolymer after, further improve temperature of reaction to 230-280 ℃, simultaneously gas clean-up makes polyglycolic acid oligopolymer generation depolymerization reaction to 10-300Pa, underpressure distillation goes out the glycollide crude product;
(4) recrystallization purifying, the glycollide crude product is being lower than under 70 ℃ the condition, heating for dissolving is in the mixed solvent by lower member ester class or lower alcohols and two kinds of solvent compositions of rudimentary ketone, be cooled to then between 45-60 ℃, in interpolation methyl alcohol, ether, methylene dichloride, Skellysolve A or the tetrahydrofuran (THF) low boiling point solvent one or several, impel the formation of glycollide nucleus in the supersaturated solution of clear, slowly be cooled to the frozen water temperature then, promptly obtain the glycollide product of purifying.
2, the preparation method of glycollide according to claim 1, catalyst system therefor is metal-powder or its oxide compound, halogenide or the hydroxy acid salt of tin or zinc in the condensation polymerization step that it is characterized in that dewatering, its add-on is the feed intake 0.1-6% of quality of oxyacetic acid.
3, the preparation method of glycollide according to claim 1, it is characterized in that catalyst system therefor is tin protochloride, stannous octoate, the inferior tin of lactic acid, methyl ethyl diketone zirconium, zinc lactate, zinc chloride, iron trichloride, iron lactate or ferric acetyl acetonade in the melt phase polycondensation step, or wherein any two or more mixture, its add-on is the feed intake 0.3%-0.7% of quality of oxyacetic acid.
4, the preparation method of glycollide according to claim 1, it is characterized in that used mixed solvent is a kind of of following combination in the recrystallization purifying step: methyl acetate and acetone, methyl acetate and butanone, ethyl acetate and acetone, ethyl acetate and butanone, methyl alcohol and acetone, methyl alcohol and butanone, ethanol and acetone or alcohol and butanone, the volume ratio of two kinds of solvents are 3: 1-9: 1.
5, the preparation method of glycollide according to claim 1, the add-on that it is characterized in that the low boiling point solvent in the recrystallization purifying step is 0.1-0.3ml.
6, the preparation method of glycollide according to claim 1 is characterized in that in the recrystallization purifying step that it is 5-10 ℃/hour that the glycollide nucleus forms the back rate of temperature fall.
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