CN105315152A - Preparation method polyglycolic acid oligomer - Google Patents
Preparation method polyglycolic acid oligomer Download PDFInfo
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- CN105315152A CN105315152A CN201410355419.9A CN201410355419A CN105315152A CN 105315152 A CN105315152 A CN 105315152A CN 201410355419 A CN201410355419 A CN 201410355419A CN 105315152 A CN105315152 A CN 105315152A
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Abstract
The invention relates to a preparation method of a polyglycolic acid oligomer. The preparation method is mainly used for solving problems of the prior art that the content of impurities is large when the polyglycolic acid oligomer prepared via a conventional method is used for producing glycolide, and glycolide yield and purity are low. The preparation method comprises following steps: (1) normal pressure condensation polymerization, wherein glycollic acid crystals are subjected to staged reaction at normal pressure in the presence of a condensation catalyst or an ester exchange catalyst, wherein normal pressure prepolymerization is carried out for 0.5 to 10h at a temperature maintained to be higher than the melting point of glycollic acid and lower than the boiling point of glycollic acid at a step of first stage prepolymerization, and condensation reaction or ester exchange is carried out at 112 to 220 DEG C until no water is evaporated for a step of second stage condensation polymerization so as to obtain a molten glycollic acid oligomer; and (2) decompression polycondensation; and (3) strengthened polycondensation. The preparation method is capable of solving the problems above preferably, and can be applied to industrial production of glycolide.
Description
Technical field
The present invention relates to a kind of production method of glycolic acid oligomer, it is prepared by polycondensation oxyacetic acid.Glycolic acid oligomer is preparation glycollide important source material, and glycollide is the most frequently used monomer of preparation high molecular polyglycolic acid.
Polycondensation sufficient reacting is made by strengthening polycondensation condition; Again the glycolic acid oligomer obtained is prepared glycollide through depolymerization, in the glycollide of gained, the content of impurity is lower.This method ensure that and obtain highly purified glycollide, simultaneously for next step refining purification is provided convenience.
Background technology
Polyglycolic acid is a kind of aliphatic polyester with excellent biodegradable and biocompatibility, is widely used in the aspects such as the stitching of the dirty repairing of the internal fixtion of human body or animal bone fracture, the reparation of Cranial defect, flesh and human body or animal blood vessels, muscle and other tissue.
Adopt the polycondensation of oxyacetic acid Direct Dehydration generally can only obtain relative molecular weight at hundreds of to the oligopolymer of several thousand, be difficult to the use properties meeting material.Glycollide is the conventional monomer of preparation high molecular polyglycolic acid.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%, the thick glycollide of gained further by solvent wash and repeatedly solvent recrystallization purify.
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 CN101054371A 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%.Obtain crude product to be purified by recrystallization, and in crystallisation process, add low boiling point solvent as nucleator, be conducive to glycolide crystals and separate out.The method is not suitable for scale operation.
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, also mention 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 and is mixed with this kind of solvent in the thick product of glycollide and is difficult to purifying.
Generally the glycollide containing impurity such as glycolic acid monomers, glycolic acid oligomer and water is called thick glycollide.In these impurity above-mentioned, glycolic acid monomers and glycolic acid oligomer are acidic components, and glycollide easily ring-opening reaction occurs under the action of an acid.The particularly existence of water, can impel glycollide to be hydrolyzed and generate acidic component.Prepare in the process of glycollide at depolymerized oligomer, the reaction of lower-molecular-weight component to preparation glycollide of glycolic acid oligomer has very material impact.This is because the low component of molecular weight is under high temperature high vacuum condition, has little time depolymerization and will be easy to steam, thus enter the product system of collection, not only can affect the purity of product, simultaneously also easy catalysis glycollide open loop, affect the yield of glycollide further.
The purity divided ring polymerization of glycollide is vital, directly determines the size of the molecular weight of polymkeric substance.At present, large quantifier elimination mainly concentrates on the refining purification aspect of glycollide.In the preparation process of glycollide, by improving technique, obtain the glycollide product that purity is higher, can refine purification to the later stage can bring great convenience, and can greatly save production cost.
Summary of the invention
The technical problem that the present invention solves is that the glycolic acid oligomer prepared in prior art is more for the production of impurity during glycollide, obtained glycollide yield and the lower problem of purity, there is provided a kind of glycolic acid oligomer preparation method for the production of glycollide, it is prepared by polycondensation oxyacetic acid.The feature of the method is: make polycondensation abundant by normal pressure segmentation polycondensation and reinforcement polycondensation condition; Again the glycolic acid oligomer obtained is prepared glycollide through depolymerization, in the glycollide of gained, the content of impurity is lower.High-purity glycollide can be prepared by the method, improve the yield of glycollide, simultaneously for next step refining purification is provided convenience.
For solving the problems of the technologies described above, the present invention by the following technical solutions: a kind of preparation method of glycolic acid oligomer, is characterized in that comprising the following steps:
(1) normal pressure polycondensation, under condensation catalyst or transesterification catalyst exist, by oxyacetic acid crystal in atmospheric conditions, segmentation is reacted: first stage pre-polymerization, be kept above the temperature of the fusing point of oxyacetic acid the boiling point lower than oxyacetic acid, prepolymerization reaction 0.5 ~ 10 hour; Subordinate phase polycondensation, at temperature of reaction 112 ~ 220 DEG C, carries out condensation reaction or transesterification reaction, till anhydrous steaming, obtains the glycolic acid oligomer of melting;
(2) decompression polycondensation, after step (1), 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;
(3) strengthen polycondensation, after step (2), holder ties up to temperature of reaction 112 ~ 220 DEG C, continues reaction 0.5 ~ 10 hour, obtain described glycolic acid oligomer under reaction pressure 0.1 ~ 5KPa.
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; The consumption of described condensation catalyst or transesterification catalyst is 0.001 ~ 10wt% of oxyacetic acid raw material dosage, is preferably 0.01 ~ 5wt%, is more preferably 0.05 ~ 1wt%, most preferably is 0.07 ~ 0.7wt%; The reaction times of described first stage pre-polymerization is preferably 0.5 ~ 5h; 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; 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; The purity of described oxyacetic acid crystal is preferably greater than 99%.
In technique scheme, the reaction times of first stage pre-polymerization is preferably 1.5 ~ 2.5h, and the reaction times strengthening polycondensation is preferably 1 ~ 2h, and the productive rate that the glycolic acid oligomer adopting this technical scheme to obtain prepares glycollide is higher.
Glycollide purity molar purity of the present invention represents, the purity of glycollide is determined by nucleus magnetic resonance (Nuclearmagneticresonance) wave spectrum, and calculation formula is: purity=[integral area/(integral area at the integral area+impurity nuclear-magnetism peak at glycollide nuclear-magnetism peak) at glycollide nuclear-magnetism peak] × 100%.
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.
Adopt technical scheme of the present invention, by controlling the reaction times of first stage pre-polymerization at 1.5 ~ 2.5h, controlling to strengthen polycondensation reaction time is 1 ~ 2h, and can reach glycollide crude product productive rate is 91%.Glycollide molar purity 84%, 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, to stopped reaction when steaming without glycollide, obtain glycollide crude product 265g, productive rate is 87%.Glycollide molar purity 59%.
[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, to stopped reaction when steaming without glycollide, obtain glycollide crude product 268g, productive rate is 88%.Glycollide molar purity 70%.
[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, to stopped reaction when steaming without glycollide, obtain glycollide crude product 265g, productive rate is 87%.Glycollide molar purity 73%.
[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, to stopped reaction when steaming without glycollide, obtain glycollide crude product 272g, productive rate is 89%.Glycollide molar purity 78%.
[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, to stopped reaction when steaming without glycollide, obtain glycollide crude product 265g, productive rate is 87%.Glycollide molar purity 80%.
[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%.Glycollide molar purity 84%.
[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, 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 6h, 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 86%.Glycollide molar purity 83%.
[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%.Glycollide molar purity 78%.
Claims (10)
1. a preparation method for glycolic acid oligomer, is characterized in that comprising the following steps:
(1) normal pressure polycondensation, under condensation catalyst or transesterification catalyst exist, by oxyacetic acid crystal in atmospheric conditions, segmentation is reacted: 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, at temperature of reaction 112 ~ 220 DEG C, carries out condensation reaction or transesterification reaction, till anhydrous steaming, obtains the glycolic acid oligomer of melting;
(2) decompression polycondensation, after step (1), 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;
(3) strengthen polycondensation, after step (2), holder ties up to temperature of reaction 112 ~ 220 DEG C, continues reaction 0.5 ~ 10 hour, obtain described glycolic acid oligomer under reaction pressure 0.1 ~ 5KPa.
2. the preparation method of glycolic acid oligomer 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. oligopolymer preparation method according to claim 1, is characterized in that the consumption of described condensation catalyst or transesterification catalyst is 0.001 ~ 10wt% of oxyacetic acid raw material dosage.
4. oligopolymer preparation method 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. oligopolymer preparation method according to claim 1, is characterized in that the reaction times of described first stage pre-polymerization is 0.5 ~ 5 hour.
6. oligopolymer preparation method according to claim 1, is characterized in that the temperature of reaction of described subordinate phase polycondensation is 140 ~ 220 DEG C.
7. oligopolymer preparation method according to claim 1, is characterized in that the reaction pressure of described decompression polycondensation is 0.1 ~ 3KPa.
8. oligopolymer preparation method according to claim 1, is characterized in that the temperature of reaction of described reinforcement polycondensation phase is 140 ~ 220 DEG C.
9. oligopolymer preparation method according to claim 1, is characterized in that the reaction pressure of described reinforcement polycondensation phase is 0.1 ~ 3KPa.
10. oligopolymer preparation method according to claim 1, is characterized in that the purity of described oxyacetic acid crystal is greater than 99%.
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Cited By (10)
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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 |
| 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 |
| 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 |
| CN114213634A (en) * | 2022-01-11 | 2022-03-22 | 内蒙古久泰新材料有限公司 | Process for continuously preparing alkyd oligomer |
| CN114478469A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Preparation method of low-water-content crude glycolide and glycolide obtained by same |
| CN114790279A (en) * | 2021-01-26 | 2022-07-26 | 惠生工程（中国）有限公司 | Industrial production process method of polyglycolic acid oligomer |
| CN115505106A (en) * | 2021-06-22 | 2022-12-23 | 上海浦景化工技术股份有限公司 | Preparation method of anti-aging polyglycolic acid |
| CN114790279B (en) * | 2021-01-26 | 2024-09-27 | 惠生工程（中国）有限公司 | Industrial production process method of polyglycolic acid oligomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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| CN114478469A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Preparation method of low-water-content crude glycolide and glycolide obtained by same |
| CN114478469B (en) * | 2020-10-26 | 2023-08-04 | 中国石油化工股份有限公司 | Preparation method of low-water-content crude glycolide and glycolide obtained by preparation method |
| CN114790279A (en) * | 2021-01-26 | 2022-07-26 | 惠生工程（中国）有限公司 | Industrial production process method of polyglycolic acid oligomer |
| CN114790279B (en) * | 2021-01-26 | 2024-09-27 | 惠生工程（中国）有限公司 | Industrial production process method of polyglycolic acid oligomer |
| CN115505106A (en) * | 2021-06-22 | 2022-12-23 | 上海浦景化工技术股份有限公司 | Preparation method of anti-aging polyglycolic acid |
| CN115505106B (en) * | 2021-06-22 | 2024-04-05 | 上海浦景化工技术股份有限公司 | Preparation method of aging-resistant polyglycolic acid |
| CN114213634A (en) * | 2022-01-11 | 2022-03-22 | 内蒙古久泰新材料有限公司 | Process for continuously preparing alkyd oligomer |
| CN114213634B (en) * | 2022-01-11 | 2023-08-11 | 内蒙古久泰新材料有限公司 | Continuous preparation process of alkyd oligomer |
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Application publication date: 20160210 |