CN103242287A - Preparation method of glycolide - Google Patents
Preparation method of glycolide Download PDFInfo
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Abstract
The invention discloses a preparation method of glycolide. According to the preparation method, high purified glycolic acid crystal is taken as a raw material, and high-purity high-yield glycolide crystal can be synthetized through a series of steps such as dehydration polycondensation, melt phase polycondensation, depolymerization reaction and recrystallization purification. Glycolic acid oligomer is generated through glycolic acid polycondensation, and almost all the glycolic acid oligomers are depolymerized for preparing the glycolide under the action of a high efficient catalyst, the usage amount of the catalyst is low, the preparation technology is simple, the yield is high and the preparation method has industrial production potential.
Description
Technical field
The present invention relates to a kind of preparation method of glycollide, belong to the ring compound preparing technical field.
Background technology
Polyglycolic acid, co-glycolic acid is because its excellent biological compatibility and biodegradability, be widely used in medicine control release field, Cosmetics Surgery, dentistry, field of tissue engineering technology etc., these complicated application requiring polymkeric substance are degraded within the predetermined time or are absorbed, and the control of degradation time need or be passed through form by primary structure characteristics such as polymer backbone and functional characteristicss, mechanical property such as tensile strength or modulus, thermal properties such as second-order transition temperature or fusing point or degradation temperature, secondary structure characteristics such as visco-elasticity such as storage modulus or consumption modulus determine, and the physicochemical property of these polymkeric substance depend on such as skeleton, constructional features such as crystal accumulation mode.
Contain-CH
2The aliphatic polyester series degradation material of-COO-segment is widely used in controlled release drug delivery system, because ester bond is in pH is 7.4 physiological environment, can not rupture under the situation of enzymic hydrolysis having yet, and in this kind polyester, alpha hydroxy acid obtains using the most widely, as polyglycolic acid and poly-lactic acid material.
1954, it is found that polyglycolic acid is a kind of high-intensity Fiber Composite Material of less energy-consumption with excellent compatibility, 1962, American Cyanamid Company utilizes polyglycolic acid to prepare the absorbable synthetic suture line of article one, called after " DEXON ", then the degradation material bio-medical is used and is studied widely.
Thereby the polyglycolic acid material can obtain different physicochemical property by different reaction materials, and the main method of synthetic polyglycolic acid commonly used has that direct condensation is synthetic, glycollide ring-opening polymerization, letex polymerization and solution polymerization.It is several thousand oligopolymer that the synthetic polyglycolic acid of oxyacetic acid polycondensation can only obtain molecular weight, and these high amorphous oligopolymer can be used thing medicine control release field.The ring-opening polymerization of glycollide is widely used in the synthetic of high-molecular-weight poly co-glycolide polymers and related copolymers, by the choose reasonable to initiator, synthesis temperature and catalyzer, can effectively control the molecular weight of polymkeric substance, thereby effectively regulate and control degradation time and the mechanical property of polymkeric substance, to satisfy the needs of bio-medical.US20070150001A1, EP1734159, EP1736498B1 have illustrated that the sutural preparation of high strength polyglycolic acid needs the polyglycolic acid raw material of high quality low-monomer-content, and oligomeric hydroxy acetic acid is difficult to meet the demands.
Except the oxyacetic acid direct condensation prepares the polyglycolic acid, the raw material of ring-opening polymerization, letex polymerization and solution polymerization all needs glycollide, and the common method for preparing glycollide has high-temperature fusion depolymerization polyglycolic acid and high boiling point solution depolymerization polyglycolic acid.CN101054371A prepares glycolide monomer by fusion depolymerization oligomeric hydroxy acetic acid, but to the purity requirement height of oxyacetic acid crystal, catalyst levels is bigger, and productivity ratio is lower.WO9302075 is with oligomeric hydroxy acetic acid polymer film, then by the good transfer of heat of design apparatus in glycolic acid oligomers, thereby prepare glycollide efficiently, but this operating process is too complicated, needs to introduce solvent to guarantee the continuity in the glycollide preparation process.The method that US5326887 and WO9215572 provide a kind of catalyst bed to prepare glycolide monomer, but reaction unit easy to clean not, and this preparation method's productive rate is lower.US4835293 and US5023349 optimize the method that will utilize rare gas element that the glycollide product is taken out of from solvent system, slow but this method prepares the speed of ring-type monoesters, and need carry out warm to a large amount of rare gas elementes, increase production cost.The US4727163 optimization thermally-stabilised center of preparation and the depolymerization of polyglycolic acid block materials prepare the method for glycollide.US5830991 and US6916939 prepare glycollide by introducing high boiling solvent reduction system viscosity and depolymerization temperature depolymerization oligomeric hydroxy acetic acid, by glycollide and high boiling solvent are distilled out to prepare glycollide efficiently simultaneously, remove but organic solvent residue is difficult in the product.
Above-mentioned patent has also been mentioned the catalyzer that adopts in this technological process.Be commonly used for 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 illustrates then that glycolic acid oligomers is introduced depolymerization catalyzer such as rare earth compounds such as tin or tin compound, yttrium, antimony compounds etc. in high temperature solution collecting process can be with at feed ratio 1.2 times of the molecular weight control of residual reactants.And CN101054371A has adopted dual catalyst depolymerization lower molecular weight polyglycolic acid to prepare glycollide, in IV, V, halogenide or the organic acid compound of condensation catalysts such as the metal of VII main group and II B subgroup or metallic compound or transesterification catalyst and tin, perhaps rare earth metal complex, perhaps zinc halogenide or organic zinc compound, perhaps under the acting in conjunction of iron halide or organoiron compound, the produced in high yields glycollide, but this method requires very high for material purity, melt phase polycondensation temperature height, the catalyst system complexity does not satisfy simple energy-conservation preparation of industrialization requirement.
At present, no matter be that solution depolymerization or fusion depolymerization oligomeric hydroxy acetic acid prepare in the technology of glycollide, preparation process is more complicated all, productive rate is generally not high, limited these preparation methods' industrial applications greatly, though above-mentioned patent disclosure the optimization of glycollide preparation process, environmental friendliness, mild condition, preparation process efficiently the glycollide Study on Preparation still be worth research.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the preparation method of a kind of purity height, glycollide that productive rate is high is provided.
The present invention solves the problems of the technologies described above the technical scheme of proposition to be: a kind of preparation method of glycollide may further comprise the steps:
1) dehydration polycondensation: be that 98% oxyacetic acid crystal is heated to 140 ~ 150 ℃ and carries out condensation reaction or transesterification reaction with purity, after reacting completely, obtain white glycolic acid oligomers;
2) melt phase polycondensation: the white glycolic acid oligomers that step 1) is obtained is warming up to 180 ~ 190 ℃ of continuation polycondensations 3 ~ 6 hours under the vacuum condition of 1KPa ~ 5KPa, until the complete fusion of glycolic acid oligomers;
3) depolymerization reaction: to step 2) add the depolymerization catalyzer in the glycolic acid oligomers of the complete fusion that obtains, the add-on of catalyzer is oxyacetic acid crystal 0.1 ~ 5% of the quality that feeds intake, improve temperature of reaction to 250 ~ 260 ℃, keep pressure simultaneously at 100 ~ 300Pa, make glycolic acid oligomers generation depolymerization reaction, underpressure distillation goes out the glycollide crude product;
4) recrystallization purifying: in one or more the solvent of the glycollide crude product heating for dissolving that step 3) is distilled out in lower member ester class or lower alcohols, the dissolving back crystallisation by cooling that refluxes, after crystal filtered, the repeated recrystallization operation obtained the glycollide crystal.
Catalyzer in the described step 3) is selected from a kind of in the following compounds: the hydroxy-acid salt of the oxide compound of the halogenide of the metal-powder of tin or zinc, tin or zinc, tin or zinc, tin or zinc; The add-on of catalyzer is oxyacetic acid 0.2 ~ 2% of the quality that feeds intake.
The preferred zinc lactate of the hydroxy-acid salt of described tin or zinc.
Solvent for use is one or more in ethyl acetate, acetone, butanone, methyl alcohol or the ethanol in the described step 4), and the ratio m/v of the thick quality product m of glycollide and solvent v is 1:2 ~ 1:1.1.
As an example but do not limit, oxyacetic acid is mainly by polycondensation dehydration preparation glycolic acid oligomers.This experiment adopts 98% oxyacetic acid crystal to prepare glycolic acid oligomers, and this highly purified oxyacetic acid can be by purification process such as recrystallization, distillations to the acquisition of purifying of commercially available oxyacetic acid solution, glycolic acid esters or hydroxyl acetate.
The high-temperature fusion polycondensation refers to that low-molecular-weight hydroxyl acetic acid oligopolymer continues the process of reaction under the high-temperature fusion condition.US5053522 points out that the optimization molecular weight that is prepared glycollide by the depolymerization of oligomeric hydroxy acetic acid is chosen in 500 ~ 800, therefore introduce the high-temperature fusion polycondensation, to adjust molecular weight and the molecular weight distribution of glycolic acid oligomers, and the fusing point of the glycolic acid oligomers that obtains should be more than 180 ℃, to guarantee the generation productive rate of glycollide.The time-optimized of high-temperature fusion polycondensation is chosen as 3 ~ 6 hours, and the melt phase polycondensation process can cause expending of the energy for a long time, molecular weight and molecular weight distribution that the sufficient time can better be regulated glycolic acid oligomers.
The depolymerization method of glycolic acid oligomers comprises fusion depolymerization, solution depolymerization, solid phase depolymerization.The present invention adopts the fusion depolymerization, and its process is that the heating glycolic acid oligomers is to the depolymerization temperature under reduced pressure, and glycollide distills from the depolymerization system, thereby collects the process of glycollide.The glycolic acid oligomers that depolymerization of the present invention is used is to prepare glycolic acid oligomers by oxyacetic acid crystal dehydration polycondensation, and further introduces the high-temperature fusion polycondensation and obtain.By this process, molecular weight and molecular weight distribution that can more effective adjusting glycolic acid oligomers, thus can in separating collecting process, carry out depolymerization reaction efficiently.
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 is by oxyacetic acid dehydration polycondensation and the high-temperature fusion polycondensation prepares glycolic acid oligomers and depolymerization prepares in the process of glycollide, material purity requires so not high, catalyzer is not introduced in the preparation of glycolic acid oligomers, little amount of catalyst is only used in the depolymerization of oligopolymer, to reach the synthetic effect of green high-efficient, and preparation technology is simple, has the potentiality of suitability for industrialized production.Reaction system is simpler, single catalyzer just, by selection of catalysts efficiently, make glycolic acid oligomers at short notice depolymerization fast prepare glycollide, shortened the time of depolymerization under the hot conditions, reduced the generation of side reaction, and saved the energy consumption in the preparation process, the productive rate height.The present invention expects that from the crystal oxyacetic acid is former the generation of the thick product of glycollide can be continuous preparation process, has shortened glycollide preparation time and technology.
Embodiment
Embodiment 1
In 150ml single port flask, add 119.1g 98% oxyacetic acid crystal, place oil bath pan, temperature is set in 140 ℃, pressure maintains 1KPa, after crystal fuses fully, there is liquid to steam gradually, behind the reaction certain hour, reactant solidifies and to be white in color, liquid stops or thing do not have obviously steam till.Keep vacuum, temperature was increased to 190 ℃ of sustained reactions 3 hours, single port receives the liquid of collecting in the flask and is clear, colorless, after the high-temperature fusion polycondensation finishes, and the system internal reaction thing state that solid and colourless liquid coexist that is white in color.Use device instead air setting device and twoport and accept flask and accept product, add the 106mg zinc lactate in system, temperature is set in 250 ℃, pressure maintains 100Pa, constantly has faint yellow glycollide crude product to steam.Treat in the system glycolic acid oligomers almost completely during depolymerization, stopped reaction gets glycollide crude product 74.1g, and productive rate is 81.5%.On Mercury VX-300 type nuclear magnetic resonance analyser, use CDCl
3Be solvent, TMS is that interior mapping is fixed, δ=4.94(H, unimodal), in δ=1.78, δ=2.12, δ=4.15, extremely weak assorted peak is on a small quantity arranged near δ=4.81, proving that thick product only contains small amount of impurities, is that 1:1.1 mix with ethyl acetate by m/v with the glycollide crude product, and heating makes the glycollide dissolving fully, obtain colourless or light yellow transparent liquid, cooling post crystallization filtration drying can obtain white glycollide crystal, and filtrate can the thick product of redissolve glycollide, and repeatedly recrystallization can obtain high purity glycollide crystal, nuclear-magnetism is characterized in δ=4.94(H, and is unimodal).
Embodiment 2
In 150ml single port flask, add 85.5g 98% oxyacetic acid crystal, place oil bath pan, temperature is set in 140 ℃, pressure maintains 3KPa, after crystal fuses fully, there is liquid to steam gradually, behind the reaction certain hour, reactant solidifies and to be white in color, liquid stops or thing do not have obviously steam till.Keep vacuum, temperature was increased to 180 ℃ of sustained reactions 5 hours, single port receives the liquid of collecting in the flask and is clear, colorless, after the high-temperature fusion polycondensation finishes, and the system internal reaction thing state that solid and colourless liquid coexist that is white in color.Use device instead air setting device and twoport and accept flask and accept product, add the 230mg zinc lactate in system, temperature is set in 250 ℃, pressure maintains 200Pa, constantly has faint yellow glycollide crude product to steam.Treat in the system glycolic acid oligomers almost completely during depolymerization, stopped reaction gets glycollide crude product 60.1g, and productive rate is 92.2%.Be that 1:1.1 mix with ethyl acetate by m/v with the glycollide crude product, heating makes the glycollide dissolving fully, obtain colourless or light yellow transparent liquid, cooling post crystallization filtration drying can obtain white glycollide crystal, filtrate can the thick product of redissolve glycollide, and repeatedly recrystallization can obtain high purity glycollide crystal.
Embodiment 3
In 150ml single port flask, add 70.3g 98% oxyacetic acid crystal, place oil bath pan, temperature is set in 140 ℃, pressure maintains 2KPa, after crystal fuses fully, there is liquid to steam gradually, behind the reaction certain hour, reactant solidifies and to be white in color, liquid stops or thing do not have obviously steam till.Keep vacuum, temperature is increased to 190 ℃ continues reaction 6 hours, single port receives the liquid of collecting in the flask and is clear, colorless, after the high-temperature fusion polycondensation finishes, and the system internal reaction thing state that solid and colourless liquid coexist that is white in color.Use device instead air setting device and twoport and accept flask and accept product, add the 300mg zinc lactate in system, temperature is set in 250 ℃, pressure maintains 300Pa, constantly has faint yellow glycollide crude product to steam.Treat in the system glycolic acid oligomers almost completely during depolymerization, stopped reaction gets glycollide crude product 51.2g, and productive rate is 95.4%.Be that 1:1.1 mix with ethyl acetate by m/v with the glycollide crude product, heating makes the glycollide dissolving fully, obtain colourless or light yellow transparent liquid, cooling post crystallization filtration drying can obtain white glycollide crystal, filtrate can the thick product of redissolve glycollide, and repeatedly recrystallization can obtain high purity glycollide crystal.
Embodiment 4
In 150ml single port flask, add 88.5g 98% oxyacetic acid crystal, place oil bath pan, temperature is set in 140 ℃, pressure maintains 2KPa, after crystal fuses fully, there is liquid to steam gradually, behind the reaction certain hour, reactant solidifies and to be white in color, liquid stops or thing do not have obviously steam till.Keep vacuum, temperature was increased to 190 ℃ of sustained reactions 7 hours 40 minutes, single port receives the liquid of collecting in the flask and is clear, colorless, after the high-temperature fusion polycondensation finishes, and the system internal reaction thing state that solid and colourless liquid coexist that is white in color.Use device instead air setting device and twoport and accept flask and accept product, add the 1.72g zinc lactate in system, temperature is set in 260 ℃, pressure maintains 200Pa, constantly has faint yellow glycollide crude product to steam.Treat in the system glycolic acid oligomers almost completely during depolymerization, stopped reaction gets glycollide crude product 62.2g, and productive rate is 92.1%.Be that 1:1.1 mix with ethyl acetate by m/v with the glycollide crude product, heating makes the glycollide dissolving fully, obtain colourless or light yellow transparent liquid, cooling post crystallization filtration drying can obtain white glycollide crystal, filtrate can the thick product of redissolve glycollide, and repeatedly recrystallization can obtain high purity glycollide crystal.
Embodiment 5
In 150ml single port flask, add 82.3g 98% oxyacetic acid crystal, place oil bath pan, temperature is set in 150 ℃, evacuated pressure maintains 5KPa, after crystal fuses fully, there is liquid to steam gradually, behind the reaction certain hour, reactant solidifies and to be white in color, liquid stops or thing do not have obviously steam till.Keep vacuum, temperature was increased to 190 ℃ of sustained reactions 3 hours, single port receives the liquid of collecting in the flask and is clear, colorless, after the high-temperature fusion polycondensation finishes, and the system internal reaction thing state that solid and colourless liquid coexist that is white in color.Use device instead air setting device and twoport and accept flask and accept product, add the 4.12g zinc lactate in system, temperature is set in 250 ℃, pressure-controlling constantly has faint yellow glycollide crude product to steam at 300Pa.Treat in the system glycolic acid oligomers almost completely during depolymerization, stopped reaction gets glycollide crude product 57.4g, and productive rate is 91.4%.Be that 1:2 mix with ethyl acetate by m/v with the glycollide crude product, heating makes the glycollide dissolving fully, obtain colourless or light yellow transparent liquid, cooling post crystallization filtration drying can obtain white glycollide crystal, filtrate can the thick product of redissolve glycollide, and repeatedly recrystallization can obtain high purity glycollide crystal.
Claims (4)
1. the preparation method of a glycollide is characterized in that, may further comprise the steps:
1) dehydration polycondensation: be that 98% oxyacetic acid crystal is heated to 140 ~ 150 ℃ and carries out condensation reaction or transesterification reaction with purity, after reacting completely, obtain white glycolic acid oligomers;
2) melt phase polycondensation: the white glycolic acid oligomers that step 1) is obtained is warming up to 180 ~ 190 ℃ of continuation polycondensations 3 ~ 6 hours under the vacuum condition of 1KPa ~ 5KPa, until the complete fusion of glycolic acid oligomers;
3) depolymerization reaction: to step 2) add the depolymerization catalyzer in the glycolic acid oligomers of the complete fusion that obtains, the add-on of catalyzer is oxyacetic acid crystal 0.1 ~ 5% of the quality that feeds intake, improve temperature of reaction to 250 ~ 260 ℃, keep pressure simultaneously at 100 ~ 300Pa, make glycolic acid oligomers generation depolymerization reaction, underpressure distillation goes out the glycollide crude product;
4) recrystallization purifying: in one or more the solvent of the glycollide crude product heating for dissolving that step 3) is distilled out in lower member ester class or lower alcohols, the dissolving back crystallisation by cooling that refluxes, after crystal filtered, the repeated recrystallization operation obtained the glycollide crystal.
2. the preparation method of glycollide according to claim 1, it is characterized in that the catalyzer in the described step 3) is selected from a kind of in the following compounds: the hydroxy-acid salt of the oxide compound of the halogenide of the metal-powder of tin or zinc, tin or zinc, tin or zinc, tin or zinc; The add-on of catalyzer is oxyacetic acid 0.2 ~ 2% of the quality that feeds intake.
3. the preparation method of glycollide according to claim 2 is characterized in that, the hydroxy-acid salt of described tin or zinc is zinc lactate.
4. the preparation method of glycollide according to claim 1, it is characterized in that, solvent for use is one or more in ethyl acetate, acetone, butanone, methyl alcohol or the ethanol in the described step 4), and the ratio m/v of the thick quality product m of glycollide and solvent v is 1:2 ~ 1:1.1.
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| CN104829586A (en) * | 2015-04-13 | 2015-08-12 | 泰兴市沃特尔化工有限公司 | New glycolide preparation method and cracking apparatus thereof |
| CN105272958A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Glycolide preparation method |
| CN105315152A (en) * | 2014-07-24 | 2016-02-10 | 中国石油化工股份有限公司 | Preparation method polyglycolic acid oligomer |
| CN105315155A (en) * | 2014-07-24 | 2016-02-10 | 中国石油化工股份有限公司 | Method used for preparing polyglycolic acid oligomer |
| CN105622567A (en) * | 2014-10-27 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method of high-yield glycolide |
| CN106397389A (en) * | 2016-09-07 | 2017-02-15 | 南京大学 | Process method for fully-green synthesis of glycolide |
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| CN107286127A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | The preparation method of low acid content 1,4- dioxane -2,5- acetyl butyryls |
| CN107868076A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The preparation of low impurity content glycolide |
| CN109438411A (en) * | 2018-10-24 | 2019-03-08 | 深圳光华伟业股份有限公司 | Glycolide process units and production method |
| CN111548339A (en) * | 2020-04-10 | 2020-08-18 | 深圳光华伟业股份有限公司 | Process for preparing glycolide from glycollate |
| CN113278005A (en) * | 2021-06-25 | 2021-08-20 | 上海东庚化工技术有限公司 | Synthetic method of high-purity glycolide |
| CN113336739A (en) * | 2021-06-25 | 2021-09-03 | 上海东庚化工技术有限公司 | Method for preparing high-purity glycolide |
| CN114149403A (en) * | 2021-11-17 | 2022-03-08 | 中国五环工程有限公司 | Mixed crystal form glycolide, and preparation method and application thereof |
| CN116410177A (en) * | 2022-08-30 | 2023-07-11 | 深圳市迈启生物材料有限公司 | Preparation method of medical glycolide |
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| CN113336739A (en) * | 2021-06-25 | 2021-09-03 | 上海东庚化工技术有限公司 | Method for preparing high-purity glycolide |
| CN114149403A (en) * | 2021-11-17 | 2022-03-08 | 中国五环工程有限公司 | Mixed crystal form glycolide, and preparation method and application thereof |
| CN114149403B (en) * | 2021-11-17 | 2024-01-26 | 中国五环工程有限公司 | Mixed crystal form glycolide and preparation method and application thereof |
| CN116410177A (en) * | 2022-08-30 | 2023-07-11 | 深圳市迈启生物材料有限公司 | Preparation method of medical glycolide |
| CN116410177B (en) * | 2022-08-30 | 2024-01-30 | 深圳市迈启生物材料有限公司 | Preparation method of medical glycolide |
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