CN105272958A - Glycolide preparation method - Google Patents
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Abstract
The present invention relates to a glycolide preparation method. A purpose of the present invention is mainly to solve the problems of low purity and low yield of the prepared glycolide in the prior art. The technical scheme comprises: (1) melt condensation polymerization: a) normal pressure condensation polymerization, wherein a glycolic acid crystal is subjected to sectional reaction under a normal pressure in the presence of a condensation catalyst or a transesterification catalyst, the reaction is performed for 0.5-10 h by maintaining the reaction temperature between the glycolic acid melting point and the glycolic acid boiling point at the first stage normal pressure prepolymerization, and at the second stage normal pressure condensation polymerization, the condensation reaction or the transesterification reaction is performed at a reaction temperature of 112-220 DEG C until no water is distilled to obtain the molten glycolic acid oligomer, b) pressure reducing condensation polymerization, and c) strengthened condensation polymerization; and (2) high temperature depolymerization, wherein a depolymerization reaction is performed at a reaction temperature of 230-290 DEG C under a reaction pressure of 0.1-1 KPa so as to obtain the glycolide crude product. With the technical scheme of the present invention, the problems in the prior art are well solved, and the method can be used in the industrial glycolide production.
Description
Technical field
The present invention relates to a kind of production method of glycollide, it is the glycolic acid oligomer prepared by oxyacetic acid polycondensation, then separates glycolic acid oligomer and prepares glycollide.Glycollide is the most important monomer of preparation high molecular polyglycolic acid.
Depolymerization be preparation glycollide must through step.During depolymerization, by controlling depolymerisation conditions, can the acquisition glycollide of high yield.The glycollide of generation can be made to steam fast by the method, decrease side reaction, ensure that the transformation efficiency that depolymehzation process is high, thus the acquisition glycollide of high yield.
Background technology
Polyglycolic acid (PGA), also known as polyglycolic acid or the acid of PVOH lactide, is business-like synthetic operating sutures the earliest.Its synthesis mainly contains the ring-opening polymerization method two kinds of oxyacetic acid direct polymerization method and glycollide.Direct polymerization method is simple to operate, but generally can only obtain the oligopolymer of relative molecular weight at hundreds of to several thousand.The ring-opening polymerization of glycollide is the common method obtaining high molecular weight PGA.
Glycollide is cyclic ester compounds, and it has the structure wherein eliminating two water moleculess from two glyclolic acid molecules, but the esterification of carrying out by means of only Direct Dehydration can not generate any glycollide.Usually, the synthesis of glycollide class monomer is divided into two steps: first synthesize low-molecular-weight polymkeric substance (hereinafter referred to as oligopolymer) as intermediate by oxyacetic acid or ethyl glycolate polycondensation; Then by the above-mentioned intermediate of pyrogenous method cyclisation to generate glycollide, and from reaction system, extract the cyclisation thing of this gaseous state.
U.S. patent 2668162 discloses a kind of method, first glycolic acid oligomer is prepared at 170 ~ 185 DEG C by melt phase polycondensation, then glycolic acid oligomer is broken into powder, and 1.6 ~ 2.0kPa, in 270 ~ 285 DEG C of heating, collects the steam that gained contains glycollide under a high vacuum.The yield of thick glycollide is the highest can reach 83%.But the method needs oligopolymer to be first broken into powder, then carries out depolymerization, and powder easily causes environmental pollution, is unfavorable for suitability for industrialized production.
U.S. patent 4727163 discloses a kind of method, uses the polyethers with good thermal stability to make base material, and then oxyacetic acid and base material carry out block copolymerization and obtain segmented copolymer, and finally heating segmented copolymer carries out depolymerization.Yield is 67%.High temperature resistant polyethers can be reused although can lead to, can as the solvent at depolymehzation process, favourable have system to be heated evenly, but need the polynary polyethers of at substantial, at high temperature polymkeric substance has a lot of side reaction generation simultaneously, obtains the impurity introducing other in glycolide product.
U.S. patent 4835293 discloses a kind of method, first glycolic acid oligomer is prepared at 170 ~ 185 DEG C by melt phase polycondensation, then depolymerization is carried out at ambient pressure, the glycollide evaporated at bath surface is entrained with by nitrogen, mixed gas is collected by water-fast non-polar solvent, yield 48% ~ 62%.Because the generating rate of cyclic dimer is comparatively slow, this method is difficult to reduce production cost
Patent CN101054371 discloses a kind of method, highly purified oxyacetic acid crystal is adopted to be raw material, glycolic acid oligomer is prepared by dehydrating polycondensation, melt phase polycondensation, oligopolymer high-temperature fusion depolymerization under the catalysis of two kinds of catalyzer of gained, the highest yield of thick glycollide can reach 86%.The method is when preparing glycollide, and reaction process is consuming time longer, is difficult to reduce production cost.
Many sections of patent US5830991 of Wu Yu company, US6891048B2, US691639B2, CN1496359A, CN1501923A, mention adopting and add in high boiling point polar organic solvent to glycolic acid oligomer to reduce reaction system viscosity and depolymerization temperature of reaction, during depolymerization, glycollide can steam together with high boiling organic solvent, well solves the problem of line clogging; Also mention simultaneously glycolic acid oligomer and polar organic solvent add depolymerization system simultaneously and introduce simultaneously divalence or multivalent cationic form vitriol and or organic acid salt stablizer to prevent the generation of side reaction.But the method result in the thick product of glycollide and is mixed with this kind of solvent, add refining difficulty of purifying.
Generally believe now, at high temperature during depolymerization, glycolic acid oligomer molecule chain end can occur back to sting reaction, and end generates six annulus unstable structures, and then generates glycollide.In depolymerization system, there is a large amount of acidic components, easily there is ring-opening reaction in glycollide under the action of an acid.Thus the glycollide generated can be extracted out fast from depolymerization system, can avoid glycollide generation ring-opening reaction, thus improves the yield of glycollide; Simultaneously, the quick decision of depolymerization reaction is due to depolymerization reaction activation energy, and activation energy is the function of temperature of reaction, impact by temperature of reaction is very large, choose suitable temperature of reaction, depolymerization reaction speed can be made very fast, Reaction time shorten, the generation of other side reaction can be reduced, thus improve the yield of glycollide.
Summary of the invention
Technical problem to be solved by this invention is the problem that the glycollide purity prepared of prior art and yield are lower, a kind of production method of glycollide is provided, it take oxyacetic acid as raw material, first prepare glycolic acid oligomer by normal pressure segmentation and reinforcement polycondensation, and then this oligopolymer of high temperature depolymerization prepares glycollide.During depolymerization, by controlling depolymerisation conditions, the vacuum tightness of especially depolymerization, can the acquisition glycollide of high yield.The glycollide of generation can be made to steam fast by the method, decrease side reaction, ensure that the transformation efficiency that depolymehzation process is high, thus the acquisition glycollide of high yield.
For solving the problems of the technologies described above, the present invention by the following technical solutions: preparation method for glycolide, comprises the following steps:
(1) melt phase polycondensation: a) normal pressure polycondensation, under condensation catalyst or transesterification catalyst exist, by the segmentation reaction in atmospheric conditions of oxyacetic acid crystal: first stage pre-polymerization, keep temperature of reaction higher than oxyacetic acid fusing point and lower than and the boiling point of oxyacetic acid between, prepolymerization reaction 0.5 ~ 10 hour; Subordinate phase polycondensation, at temperature of reaction 112 DEG C ~ 220 DEG C, carries out condensation reaction or transesterification reaction, till anhydrous steaming, obtains the glycolic acid oligomer of melting; B) reduce pressure polycondensation, step a) after, holder ties up to temperature of reaction 112 ~ 220 DEG C, under reaction pressure 0.1 ~ 5KPa, condensation reaction or transesterification reaction is proceeded, until do not have water to steam; C) polycondensation is strengthened, in step b) after, holder ties up to temperature of reaction 112 ~ 220 DEG C, continues reaction 0.5 ~ 10 hour under reaction pressure 0.1 ~ 5KPa.
(2) high temperature depolymerization, after step (1), by system temperature of reaction 230 ~ 290 DEG C, reaction pressure 0.1 ~ 1KPa, makes glycolic acid oligomer generation depolymerization reaction, and then underpressure distillation obtains glycollide crude product.
In technique scheme, preferred version is: described condensation catalyst or transesterification catalyst are preferably at least one in the organic acid compound of the halogenide of tin, tin, or/and at least one in the organic acid compound of the halogenide of the oxide compound of antimony, antimony, antimony, or/and at least one in the title complex of the organic compound of the halogenide of the oxide compound of zinc, zinc, zinc, zinc, or/and at least one in the title complex of organo-aluminium compound, aluminium, or/and at least one in rare earth metal complex; Described condensation catalyst or the consumption of transesterification catalyst are 0.001 ~ 10wt% of oxyacetic acid material quantity, are preferably 0.01 ~ 5wt%, are more preferably 0.05 ~ 1wt%, most preferably are 0.07 ~ 0.7wt%.In normal pressure polycondensation, the reaction times of described first stage pre-polymerization is preferably 1 ~ 5 hour; The temperature of reaction of described subordinate phase polycondensation is preferably 140 ~ 220 DEG C.The reaction pressure of described decompression polycondensation is preferably 0.1 ~ 3KPa.Strengthen polycondensation phase, the temperature of reaction of described reinforcement polycondensation is preferably 140 ~ 220 DEG C, and be more preferably 160 ~ 210 DEG C, reaction pressure is preferably 0.1 ~ 3KPa, and the reaction times is preferably 0.5 ~ 6 hour.In high temperature depolymehzation step, the temperature of reaction of high temperature depolymerization is preferably 230 ~ 260 DEG C; The reaction pressure of high temperature depolymerization is preferably 0.1 ~ 0.5KPa; The reaction times of high temperature depolymerization is preferably 1 ~ 10 hour, is more preferably 2 ~ 6 hours.The purity of described oxyacetic acid crystal is preferably greater than 99%.
In technique scheme, the reaction times of first stage pre-polymerization most preferably is 1.5 ~ 2.5h, and the reaction times strengthening polycondensation most preferably is 1 ~ 2h, and the productive rate that the glycolic acid oligomer adopting this technical scheme to obtain prepares glycollide is higher.
The invention has the advantages that: when preparing glycolic acid oligomer, experienced by normal pressure staged reaction and decompression polycondensation, oxyacetic acid raw material can sufficient reacting, improve feed stock conversion, and by strengthening the technical scheme of polycondensation further, reaction times is 0.5 ~ 5 constantly little, the molecular weight being conducive to oligopolymer improves in the molten state further, and make molecular weight distribution more homogeneous by transesterification reaction, thus depolymerization is stablized, in the glycollide generated, foreign matter content is low, and glycollide yield is higher; And when preparing glycollide, at depolymerization, by choosing suitable de-polymerization temperature, reducing depolymerization system and obtaining vacuum tightness, can effectively impel glycollide to steam fast, Reaction time shorten, reducing the generation of side reaction, improving the yield of glycollide.
Adopt technical scheme of the present invention, especially the reaction times of first stage normal pressure pre-polymerization is adopted to be preferably 1.5 ~ 2.5h, the reaction times strengthening polycondensation is preferably the technical scheme of 1 ~ 2h, temperature of reaction 230 ~ 290 DEG C, reaction pressure 0.1 ~ 1KPa, makes glycolic acid oligomer generation depolymerization reaction, and then underpressure distillation obtains glycollide crude product, productive rate can reach 91%, achieves good technique effect.
Further illustrate below by specific embodiment.
Embodiment
Embodiments of the present invention and effect is further illustrated by following indefiniteness example.
[embodiment 1]
Add 400g oxyacetic acid crystal and 2g stannous octoate catalyst in reactor after, temperature rises to 90 DEG C, after solid dissolves completely from room temperature, be warming up to 112 DEG C and start pre-polymerization, be warming up to 140 DEG C after pre-polymerization 1h, after anhydrous steaming, system keeps temperature and starts to vacuumize.This process vacuum degree control is at 3KPa.After anhydrous steaming, system keeps this state to continue reaction 1h, obtains glycolic acid oligomer 311g.
By the glycolic acid oligomer that obtains temperature of reaction 260 DEG C, under vacuum tightness 0.5KPa, carry out reaction preparation glycollide, react stopped reaction after 10 hours, obtain glycollide crude product 265g, productive rate is 87%.
[embodiment 2]
Add 400g oxyacetic acid crystal and 2g stannous octoate catalyst in reactor after, temperature rises to 90 DEG C, after solid dissolves completely from room temperature, be warming up to 112 DEG C and start pre-polymerization, be warming up to 160 DEG C after pre-polymerization 1h, after anhydrous steaming, system keeps temperature and starts to vacuumize.This process vacuum degree control is at 3KPa.After anhydrous steaming, system keeps this state to continue reaction 1h, obtains glycolic acid oligomer 308g.
By the glycolic acid oligomer that obtains temperature of reaction 260 DEG C, under vacuum tightness 0.5KPa, carry out reaction preparation glycollide, react stopped reaction after 10 hours, obtain glycollide crude product 268g, productive rate is 88%.
[embodiment 3]
Add 400g oxyacetic acid crystal and 2g stannous octoate catalyst in reactor after, temperature rises to 90 DEG C, after solid dissolves completely from room temperature, be warming up to 112 DEG C and start pre-polymerization, be warming up to 180 DEG C after pre-polymerization 1h, after anhydrous steaming, system keeps temperature and starts to vacuumize.This process vacuum degree control is at 3KPa.After anhydrous steaming, system keeps this state to continue reaction 1h, obtains glycolic acid oligomer 300g.
By the glycolic acid oligomer that obtains temperature of reaction 260 DEG C, under vacuum tightness 0.5KPa, carry out reaction preparation glycollide, react stopped reaction after 10 hours, obtain glycollide crude product 265g, productive rate is 87%.
[embodiment 4]
Add 400g oxyacetic acid crystal and 2g stannous octoate catalyst in reactor after, temperature rises to 90 DEG C, after solid dissolves completely from room temperature, be warming up to 112 DEG C and start pre-polymerization, be warming up to 200 DEG C after pre-polymerization 2h, after anhydrous steaming, system keeps temperature and starts to vacuumize.This process vacuum degree control is at 3KPa.After anhydrous steaming, system keeps this state to continue reaction 1h, obtains glycolic acid oligomer 295g.
By the glycolic acid oligomer that obtains temperature of reaction 260 DEG C, under vacuum tightness 0.5KPa, carry out reaction preparation glycollide, react stopped reaction after 10 hours, obtain glycollide crude product 272g, productive rate is 89%.
[embodiment 5]
Add 400g oxyacetic acid crystal and 2g stannous octoate catalyst in reactor after, temperature rises to 90 DEG C, after solid dissolves completely from room temperature, be warming up to 112 DEG C and start pre-polymerization, be warming up to 200 DEG C after pre-polymerization 1h, after anhydrous steaming, system keeps temperature and starts to vacuumize.This process vacuum degree control is at 3KPa.After anhydrous steaming, system keeps this state to continue reaction 1.5h, obtains glycolic acid oligomer 291g.
By the glycolic acid oligomer that obtains temperature of reaction 260 DEG C, under vacuum tightness 0.5KPa, carry out reaction preparation glycollide, react stopped reaction after 10 hours, obtain glycollide crude product 265g, productive rate is 87%.
[embodiment 6]
Add 400g oxyacetic acid crystal and 2g stannous octoate catalyst in reactor after, temperature rises to 90 DEG C, after solid dissolves completely from room temperature, be warming up to 112 DEG C and start pre-polymerization, be warming up to 200 DEG C after pre-polymerization 2h, after anhydrous steaming, system keeps temperature and starts to vacuumize.This process vacuum degree control is at 3KPa.After anhydrous steaming, system keeps this state to continue reaction 1.5h, obtains glycolic acid oligomer 290g.
By the glycolic acid oligomer that obtains temperature of reaction 260 DEG C, under vacuum tightness 0.5KPa, carry out reaction preparation glycollide, to stopped reaction when steaming without glycollide, obtain glycollide crude product 278g, productive rate is 91%.
[embodiment 7]
Add 400g oxyacetic acid crystal and 2g stannous octoate catalyst in reactor after, temperature rises to 90 DEG C, after solid dissolves completely from room temperature, be warming up to 112 DEG C and start pre-polymerization, heat up 200 DEG C after pre-polymerization 2h, after anhydrous steaming, system keeps temperature and starts to vacuumize.This process vacuum degree control is at 3KPa.After anhydrous steaming, system keeps this state to continue reaction 1.5.
By the glycolic acid oligomer that obtains temperature of reaction 260 DEG C, under vacuum tightness 0.5KPa, carry out reaction preparation glycollide, react after 4 hours and terminate to react, obtain glycollide crude product 278g, productive rate is 91%.
[comparative example 1]
According to the method that embodiment 4 in CN101054371A patent provides, carry out the preparation of glycollide.Glycollide crude yield is 85%.
Claims (10)
1. a preparation method for glycolide, is characterized in that comprising the following steps:
(1) melt phase polycondensation: a) normal pressure polycondensation, under condensation catalyst or transesterification catalyst exist, by the segmentation reaction in atmospheric conditions of oxyacetic acid crystal: first stage pre-polymerization, keep temperature of reaction between the fusing point and the boiling point of oxyacetic acid of oxyacetic acid, prepolymerization reaction 0.5 ~ 10 hour; Subordinate phase polycondensation, temperature of reaction 112 ~ 220 DEG C, carries out condensation reaction or transesterification reaction, till anhydrous steaming, obtains the glycolic acid oligomer of melting; B) reduce pressure polycondensation, step a) after, holder ties up to temperature of reaction 112 ~ 220 DEG C, under reaction pressure 0.1 ~ 5KPa, condensation reaction or transesterification reaction is proceeded, until do not have water to steam; C) polycondensation is strengthened, in step b) after, holder ties up to temperature of reaction 112 ~ 220 DEG C, continues reaction 0.5 ~ 10 hour under reaction pressure 0.1 ~ 5KPa;
(2) high temperature depolymerization, after step (1), by system temperature of reaction 230 ~ 290 DEG C, under reaction pressure 0.1 ~ 1KPa, make glycolic acid oligomer generation depolymerization reaction, then underpressure distillation obtains glycollide crude product.
2. preparation method for glycolide according to claim 1, it is characterized in that described condensation catalyst or transesterification catalyst are at least one in the organic acid compound of the halogenide of tin, tin, or/and at least one in the organic acid compound of the halogenide of the oxide compound of antimony, antimony, antimony, or/and at least one in the title complex of the organic compound of the halogenide of the oxide compound of zinc, zinc, zinc, zinc, or/and at least one in the title complex of organo-aluminium compound, aluminium, or/and at least one in rare earth metal complex.
3. preparation method for glycolide according to claim 1, is characterized in that the consumption of condensation catalyst used or transesterification catalyst is 0.001 ~ 10wt% of oxyacetic acid raw material dosage.
4. preparation method for glycolide according to claim 1, is characterized in that the consumption of described condensation catalyst or transesterification catalyst is 0.01 ~ 5wt% of oxyacetic acid raw material dosage.
5. preparation method for glycolide according to claim 1, it is characterized in that the temperature of reaction of first stage pre-polymerization is between the fusing point and boiling point of oxyacetic acid, the reaction times is 0.5 ~ 5 hour.
6. preparation method for glycolide according to claim 1, is characterized in that the purity of described oxyacetic acid crystal is greater than 99%.
7. preparation method for glycolide according to claim 1, is characterized in that the temperature of reaction of described subordinate phase polycondensation is 140 ~ 220 DEG C.
8. preparation method for glycolide according to claim 1, is characterized in that the reaction pressure of described decompression polycondensation is 0.1 ~ 3KPa.
9. preparation method for glycolide according to claim 1, is characterized in that the temperature of reaction of described reinforcement polycondensation phase is 140 ~ 220 DEG C.
10. preparation method for glycolide according to claim 1, is characterized in that the reaction times of high temperature depolymerization is 1 ~ 10 hour.
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| CN106397389A (en) * | 2016-09-07 | 2017-02-15 | 南京大学 | Process method for fully-green synthesis of glycolide |
| CN107151238A (en) * | 2016-03-05 | 2017-09-12 | 李坚 | Formates or method and application that carbonate is Material synthesis glycolide and glycolic acid oligomer |
| CN107286126A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | The preparation method of 1,4- dioxane -2,5- acetyl butyryls |
| 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 |
| CN110684011A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Process for preparing glycolide |
| WO2020087221A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Controlled production of polyglycolic acid and glycolide |
| WO2020087217A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Glycolide production from methyl polyglycolate |
| 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 |
| CN112707884A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Glycolide and preparation method and application thereof |
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| CN114524796A (en) * | 2022-02-23 | 2022-05-24 | 中国科学院长春应用化学研究所 | Preparation method of glycolide |
| CN114671846A (en) * | 2021-12-21 | 2022-06-28 | 上海中化科技有限公司 | Process for the synthesis of glycolide |
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| CN107151238A (en) * | 2016-03-05 | 2017-09-12 | 李坚 | Formates or method and application that carbonate is Material synthesis glycolide and glycolic acid oligomer |
| 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 |
| CN107286126A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | The preparation method of 1,4- dioxane -2,5- acetyl butyryls |
| JP2019529532A (en) * | 2016-09-07 | 2019-10-17 | 南京大学Ｎａｎｊｉｎｇ Ｕｎｉｖｅｒｓｉｔｙ | Glycolide synthesis method |
| WO2018045941A1 (en) * | 2016-09-07 | 2018-03-15 | 南京大学 | Method for synthesizing glycolide |
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| 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 |
| CN110684011A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Process for preparing glycolide |
| CN110684011B (en) * | 2018-07-06 | 2021-02-09 | 中国石油化工股份有限公司 | Process for preparing glycolide |
| WO2020087221A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Controlled production of polyglycolic acid and glycolide |
| WO2020087217A1 (en) * | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Glycolide production from methyl polyglycolate |
| US11814474B2 (en) | 2018-10-29 | 2023-11-14 | Pujing Chemical Industry Co., Ltd. | Controlled production of polyglycolic acid and glycolide |
| AU2018448137B2 (en) * | 2018-10-29 | 2022-05-19 | Pujing Chemical Industry Co., Ltd | Glycolide production from methyl polyglycolate |
| CN112707884B (en) * | 2019-10-24 | 2022-07-12 | 中国石油化工股份有限公司 | Glycolide and preparation method and application thereof |
| CN112707884A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Glycolide and preparation method and application thereof |
| 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 |
| WO2022089413A1 (en) | 2020-10-26 | 2022-05-05 | 中国石油化工股份有限公司 | Method for refining glycolide and glycolide obtained using same |
| CN114671846A (en) * | 2021-12-21 | 2022-06-28 | 上海中化科技有限公司 | Process for the synthesis of glycolide |
| CN114524796A (en) * | 2022-02-23 | 2022-05-24 | 中国科学院长春应用化学研究所 | Preparation method of glycolide |
| CN114524796B (en) * | 2022-02-23 | 2024-03-26 | 中国科学院长春应用化学研究所 | Preparation method of glycolide |
| CN115536629A (en) * | 2022-10-18 | 2022-12-30 | 山东寿光巨能金玉米开发有限公司 | Preparation method of high-purity glycolide |
| CN115536629B (en) * | 2022-10-18 | 2024-03-22 | 山东寿光巨能金玉米开发有限公司 | Preparation method of glycolide |
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Application publication date: 20160127 |