CN107868074A - The method of purification of glycolide - Google Patents
The method of purification of glycolide Download PDFInfo
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- CN107868074A CN107868074A CN201610850811.XA CN201610850811A CN107868074A CN 107868074 A CN107868074 A CN 107868074A CN 201610850811 A CN201610850811 A CN 201610850811A CN 107868074 A CN107868074 A CN 107868074A
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- glycolide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
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Abstract
The present invention relates to a kind of method of purification of glycolide, mainly solves the problems, such as that the impurity of macromolecule in recrystallization process existing for prior art is difficult to remove.By using the process for purification of glycolide, comprise the following steps：1) the glycolide crude product that depolymerization reaction obtains is dissolved in solvent I, is filtered to remove insoluble matter；2) solvent I is distilled off in the filtrate being collected into heating, obtains the thick glycolide of solid phase；3) the thick glycolide obtained in step 2) is mixed with solvent II, stirred, solidliquid mixture is then collected by filtration filter cake, filter cake is dried in vacuo after repeating the operation at least 3 times, obtains refined glycolide product；Wherein, the solvent I is at least one of dichloromethane, tetrahydrofuran, acetone, ethyl acetate, Isosorbide-5-Nitrae dioxane；The solvent II is the technical scheme of at least one of alcohols, ethers, esters, ketone, preferably solves the problem, available in glycolide industrialized production.
Description
Technical field
The present invention relates to a kind of method for purifying glycolide.
Background technology
Glycolide be by the cyclic ester of two molecules of ethanol acid dehydration generation, it be it is a kind of can be used for preparing polyglycolic acid and its
The important compound of copolymer.Polyglycolic acid and its copolymer have biodegradability, can finally degrade to obtain titanium dioxide
Carbon and water, and gas barrier property and mechanical strength, in operation suture thread, artificial organ, controlled drug delivery system etc.
Biomedical materials field is widely applied.Therefore, the research for polyglycolic acid and glycolide attracts in recent years
Extensive concern.
To obtain the polyglycolic acid of HMW, it is necessary to by the use of glycolic as raw material, second is obtained by two-step reaction and handed over
Ester.It is tens of thousands of polyglycolic acids to hundreds of thousands that can obtain molecular weight using glycolide ring-opening polymerisation.One kind is exemplified below by second
The method that alkyd prepares glycolide：
(1) at ambient pressure glycolic is gradually heated to carry out polycondensation reaction not higher than 180 DEG C first and elimination reaction is given birth to
Into water, further remove moisture (generally less than 15mmHg) at reduced pressure conditions again after water yield reaches to a certain degree
Obtain the higher polycondensation product of molecular weight.
(2) at reduced pressure conditions (generally less than 5mmHg), by glycolic prepolymer and catalyst, such as stannous chloride, one
With being heated to 230 DEG C to 280 DEG C, reaction generation glycolide steam is collected, the solid crude product of yellow, this patent are obtained after cooling
Referred to as thick glycolide.
The various impurity such as water, glycolic, glycolic acid oligomer are typically include in thick glycolide obtained by above-mentioned reaction, are needed
The glycolide that purity meets polymerization demand can be obtained by purification.
The method of purification of the glycolide of patent report includes solvent absorption, evaporation method of air aided, recrystallization method etc. at present.
The more method for recrystallization is wherein used, relatively conventional is to thick using organic solvents such as isopropanol or ethyl acetate
The method that glycolide is recrystallized repeatedly.Such as patent US5223630, CN100999516, CN101054371 is handed over second
The recrystallization method of purification of ester is reported.
The method of recrystallization can effectively remove small molecular weight impurity present in thick glycolide, but companion in depolymerization reaction
As what glycolide gasified together also has the relatively large glycolic acid oligomer of molecular weight.Such impurity shows at different temperatures
Dissolubility difference out is big compared with glycolide, i.e., at high temperature have certain solubility and solubility is extremely low at room temperature.Cause
This is difficult to separate from glycolide by the method for recrystallization.The impurity of such macromolecule is mostly the polymerization of glycolic
Thing, the polymerization that the active hydrogen of its end carboxyl institute band can be to glycolide produce inhibition.Pole in the ring opening polymerisation process of glycolide
A small amount of active hydrogen presence can all produce a very large impact to the molecular weight of resulting polymers, and need to meet that operation suture thread etc. is used
The polyglycolic acid of way demand is required for meeting that intrinsic viscosity is more than or equal to 1, and matter average molecular weight is more than 100,000 requirement.Therefore, such as
What removes these impurity as the major issue in glycolide process for refining.
Pfizer reports in patent US4650851 and first glycolide is dissolved in dichloromethane, then and neutral oxygen
Change the method for filtering after aluminium mixes, solvent being evaporated off, this method is cumbersome, it is difficult to amplify, and acids impurity content reduces
There are much relations with the time is mixed, be difficult to control.Separately there are some patent reports another by being added in depolymerization reaction
Planting material and glycolic acid oligomer response inhabitation, it enters the method for thick glycolide to control the report of product acid content, such as Mitsubishi
Chemistry reports in patent US5900491 to be added the method for orthoformate in depolymerization and suppresses acids impurity in crude lactide
The method of content, but prepare relevant report without with glycolide.E.I.Du Pont Company is also reported using poly- in patent US4835293
The report of the ratio of oligomer impurity is reduced after glycolic and polyether reactant acquisition block copolymer, but can these methods be applied
All do not had been reported that in commercial scale.
The content of the invention
Problem to be solved by this invention is the problem of impurity of larger molecular weight in glycolide crude product is difficult to separation, is carried
For a kind of method of purification of glycolide, by using two kinds of different solvents purifying crude glycolides, preferably by glycolide crude product
The impurity of middle larger molecular weight is separated, and has the advantages of easy to operate, purification efficiency is high.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of method of purification of glycolide, bag
Include：
(1) the glycolide crude product that depolymerization reaction obtains is dissolved in solvent I, is filtered to remove insoluble matter；
(2) solvent I is distilled off in the filtrate being collected into heating, obtains the thick glycolide of solid phase；
(3) the thick glycolide obtained in step (2) is mixed with solvent II, stirred, then by solidliquid mixture mistake
Filter cake is collected in filter, is dried in vacuo filter cake after repeating the operation at least 3 times, is obtained refined glycolide product；
Wherein, the solvent I be dichloromethane, tetrahydrofuran, acetone, ethyl acetate, in Isosorbide-5-Nitrae-dioxane at least
It is a kind of；The solvent II is at least one of alcohols, ethers, esters, ketone.
In above-mentioned technical proposal, the solvent I is preferably dichloromethane, tetrahydrofuran, acetone, ethyl acetate, Isosorbide-5-Nitrae-two
Two or more mixture I in the ring of oxygen six；Contain acetone, the volume fraction of acetone in further preferably described mixture I
Not less than 50%.
In above-mentioned technical proposal, the solvent I is preferably dichloromethane, tetrahydrofuran, acetone, ethyl acetate, Isosorbide-5-Nitrae-two
During two or more mixture I in the ring of oxygen six, two or more solvents can play a part of collaboration purification, glycolide after refining
In content of carboxyl end group can be a kind of situation much smaller than solvent I, such as acetone and ethyl acetate volume ratio 1:1 mixture
I；Even when acetone and ethyl acetate volume ratio 1:When 1 mixture I combines with the solvent II selected from absolute ethyl alcohol, effect is more
It is good.
In above-mentioned technical proposal, solvent for use I volumetric usage is preferably to dissolve the desired amount of 1.1-2 of thick glycolide
Times.
In above-mentioned technical proposal, solvent I is distilled off preferably in inertia in the filtrate being collected into heating described in step (2)
Carried out under gas shield.
In above-mentioned technical proposal, the solvent II is preferably the two or more mixing in alcohols, ethers, esters, ketone
Thing II；Solvent II described further is preferably the mixture of alcohols and ethyl acetate or alcohols and acetone；More preferably methanol,
Ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, n-butyl ether, the mixture of MEK and ethyl acetate.
In above-mentioned technical proposal, the dosage of the solvent II is preferably 1-2 times of thick glycolide quality.
In above-mentioned technical proposal, the mixing time of thick glycolide and solvent II is preferably 0.5-3h in step (3)；Stir
Mixing process preferably has inert gas shielding.
In above-mentioned technical proposal, in the step (3) the vacuum drying time be preferably no less than 4h.
In above-mentioned technical proposal, " inert gas " can be one kind in various inert gases commonly used in the art,
Such as nitrogen, helium, argon gas.
The impurity of macromolecule is usually the glycolic acid oligomer that the degree of polymerization is more than or equal to 4 in glycolide, therefore utilizes survey
The removal effect of HMW impurity in glycolide can be characterized by determining the method for content of carboxyl end group in glycolic.Utilize acid base titration
Method can determine the content for refining end carboxyl in front and rear glycolide.Its operation is described as follows.Glycolide sample is dissolved
In 20mL or so drying dimethyl sulfoxide (DMSO), few drops of bromophenol blue indicator solution are instilled thereto after its dissolving, solution is in
Yellow.It is titrated using the benzyl alcohol solution for the sodium hydroxide that concentration is 0.01632mol/L, solution colour is by yellow
It is terminal to be changed into during green.The volume of sodium hydroxide solution used is calculated in glycolide when reaching titration end-point by calculating
Content of carboxyl end group.
Using technical scheme, the content of carboxyl end group after refining in glycolide is 8.96 × 10-6mol.g-1.Far
Less than the impurity content of macromolecule in the prior art, preferable technique effect is achieved.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
400g glycolics are added into three-necked flask, being heated to 90 DEG C under normal pressure makes reactant melt completely, afterwards in 2h
It is interior that system is warming up to 200 DEG C from 90 DEG C, and 2h is reacted at such a temperature, the water generated in reaction is distilled off during this period.
It is subsequently vacuumed out reducing system pressure to 5kPa, continues reaction 2h and be solidified into milky to reactant, obtain glycolic acid oligomer.
2.0g stannous octoates are added into oligomer, are warming up to 260 DEG C, improve vacuum to 100pa.As reaction is carried out, constantly have
Light yellow liquid is distilled out of, and yellow solid, the i.e. thick glycolide of product are obtained after cooling.Stop reaction after 3h, collect crude product, meter
Calculate yield be 92%.It is 7.90 × 10 that the content of carboxyl end group in thick glycolide is measured using acid base titration-4mol.g-1。
The thick glycolide of product (280g) is dissolved in 600g acetone, is stirred at room temperature to formation homogeneous transparent solution,
Powdery insoluble matter is filtered to remove with quartzy sand hopper.Most solvents are removed using Rotary Evaporators after filtrate is collected, will
Remove solvent after solid be added in round-bottomed flask and add 250g absolute ethyl alcohols, with after mechanical agitation 1h with quartzy sand hopper
Filtered, filter to being transferred to filter cake again after half-dried in flask and add 250g absolute ethyl alcohols and be stirred 1h.Repetition is washed
The solid being collected into is dried in vacuo 5h at 60 DEG C after the step of washing-filtering three times, obtains white crystal 216g, adds up to yield
For 70.8%.It is 1.48 × 10 to measure the content of carboxyl end group in refined rear glycolide using acid base titration-5mol.g-1。
【Embodiment 2】
The preparation of thick glycolide is the same as embodiment 1.
The thick glycolide of product (277g) is dissolved in 600g acetone, is stirred at room temperature to formation homogeneous transparent solution,
Powdery insoluble matter is filtered to remove with quartzy sand hopper.Most solvents are removed using Rotary Evaporators after filtrate is collected, will
Remove solvent after solid be added in round-bottomed flask and add 250g absolute methanols, with after mechanical agitation 1h with quartzy sand hopper
Filtered, filter to being transferred to filter cake again after half-dried in flask and add 250g absolute methanols and be stirred 1h.Repetition is washed
The solid being collected into is dried in vacuo 5h at 60 DEG C after the step of washing-filtering three times, obtains white crystal 221g, adds up to yield
For 72.3%.It is 1.15 × 10 to measure the content of carboxyl end group in refined rear glycolide using acid base titration-5mol.g-1。
【Embodiment 3】
The preparation of thick glycolide is the same as embodiment 1.
The thick glycolide of product (278g) is dissolved in the in the mixed solvent of 400g acetone and 400g ethyl acetate, in room temperature
Lower stirring is filtered to remove powdery insoluble matter to homogeneous transparent solution is formed with quartzy sand hopper.Rotation is utilized after filtrate is collected
Evaporimeter removes most solvents, and the solid after removing solvent is added in round-bottomed flask and adds 250g absolute ethyl alcohols,
Filtered with after mechanical agitation 1h with quartzy sand hopper, filter to being transferred to filter cake in flask again after half-dried and add 250g
Absolute ethyl alcohol is stirred 1h.The solid being collected into is dried in vacuo 5h at 60 DEG C after the step of repeated washing-filtering three times,
White crystal 212g is obtained, it is 69.6% to add up to yield.The content of carboxyl end group in refined rear glycolide is measured using acid base titration
For 8.96 × 10-6mol.g-1。
【Embodiment 4】
The preparation of thick glycolide is the same as embodiment 1.
The thick glycolide of product (280g) is dissolved in the in the mixed solvent of 400g acetone and 400g ethyl acetate, in room
The lower stirring of temperature is filtered to remove powdery insoluble matter to homogeneous transparent solution is formed with quartzy sand hopper.Rotation is utilized after filtrate is collected
Turn evaporimeter and remove most solvents, the solid after removing solvent is added in round-bottomed flask and adds 250g without water beetle
Alcohol, filtered with after mechanical agitation 1h with quartzy sand hopper, filter to being transferred to filter cake in flask again after half-dried and add
250g absolute methanols are stirred 1h.By the solid being collected into, vacuum is done at 60 DEG C after the step of repeated washing-filtering three times
Dry 5h, white crystal 214g is obtained, it is 70.2% to add up to yield.The end carboxyl in refined rear glycolide is measured using acid base titration
Content is 1.01 × 10-5mol.g-1。
【Comparative example 1】
The preparation of thick glycolide is the same as embodiment 1.
The thick glycolide 278g of gained is recrystallized with 400mL ethyl acetate, 70 DEG C is heated to and obtains settled solution
Heat filtering afterwards, obtained filtrate is stood and is cooled to room temperature.Repeat to tie again after the solidliquid mixture of precipitation crystal is filtered, dried
Brilliant process three times.Obtained solid is dried in vacuo 5h at 60 DEG C, obtains white crystal 187g, adds up to yield 61.2%.Profit
It is 1.36 × 10 to measure the content of carboxyl end group in refined rear glycolide with acid base titration-4mol.g-1。
【Comparative example 2】
The preparation of thick glycolide is the same as embodiment 1.
Use mechanical agitation 1h after the thick glycolide 278g of gained is mixed with 400g absolute ethyl alcohols, stirring filtered after terminating to
It is half-dried, filter cake is mixed with 250g absolute ethyl alcohols again.By obtained solid at 60 DEG C after the step of repeated washing-filtering three times
Lower vacuum drying 5h, obtains white crystal 227g, adds up to yield 74.2%.Measured using acid base titration in refined rear glycolide
Content of carboxyl end group is 9.77 × 10-5mol.g-1。
Claims (10)
1. a kind of process for purification of glycolide, comprises the following steps：
(1) the glycolide crude product that depolymerization reaction obtains is dissolved in solvent I, is filtered to remove insoluble matter；
(2) solvent I is distilled off in the filtrate being collected into heating, obtains the thick glycolide of solid phase；
(3) the thick glycolide obtained in step (2) is mixed with solvent II, stirred, then solidliquid mixture is filtered and received
Collect filter cake, filter cake is dried in vacuo after repeating the operation at least 3 times, obtains refined glycolide product；
Wherein, the solvent I is at least one of dichloromethane, tetrahydrofuran, acetone, ethyl acetate, Isosorbide-5-Nitrae-dioxane；
The solvent II is at least one of alcohols, ethers, esters, ketone.
2. the process for purification of glycolide as claimed in claim 1, it is characterised in that the solvent I is dichloromethane, tetrahydrochysene furan
Mutter, the two or more mixture I in acetone, ethyl acetate, 1,4- dioxane.
3. the process for purification of glycolide as claimed in claim 2, it is characterised in that contain acetone in described mixture I, third
The volume fraction of ketone is not less than 50%.
4. the process for purification of glycolide as claimed in claim 1, it is characterised in that solvent for use I volumetric usage is thick for dissolving
1.1-2 times of the amount of glycolide.
5. the process for purification of glycolide as claimed in claim 1, it is characterised in that the filtrate that will be collected into described in step (2)
Heating is distilled off solvent I and carried out under inert gas shielding.
6. the process for purification of glycolide as claimed in claim 1, it is characterised in that the solvent II be alcohols, ethers, esters,
Two or more mixtures IIs in ketone.
7. the process for purification of glycolide as claimed in claim 6, it is characterised in that the solvent II is alcohols and ethyl acetate
Or the mixture of alcohols and acetone；More preferably methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, n-butyl ether,
The mixture of MEK and ethyl acetate.
8. the process for purification of glycolide as claimed in claims 6 or 7, it is characterised in that the dosage of the solvent II is handed over for thick second
1-2 times of ester quality.
9. the process for purification of glycolide as claimed in claim 1, it is characterised in that thick glycolide and solvent II in step (3)
The mixing time is 0.5-3h；Whipping process has inert gas shielding.
10. the process for purification of glycolide as claimed in claim 1, it is characterised in that when vacuum drying in the step (3)
Between be no less than 4h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087381A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Refining treatment method of glycolide |
| CN114014835A (en) * | 2021-12-09 | 2022-02-08 | 内蒙古久泰新材料有限公司 | Glycolide purification process |
| 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 |
| 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 |
| CN114790188A (en) * | 2021-01-26 | 2022-07-26 | 惠生工程（中国）有限公司 | Refining and purifying method of crude glycolide |
| CN115246812A (en) * | 2021-04-28 | 2022-10-28 | 上海浦景化工技术股份有限公司 | Method for refining glycolide |
| CN115246811A (en) * | 2021-04-28 | 2022-10-28 | 上海浦景化工技术股份有限公司 | Continuous production method of purified glycolide |
| CN115504957A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Glycolide refining method and glycolide obtained by same |
| CN116283888A (en) * | 2022-08-30 | 2023-06-23 | 深圳市迈启生物材料有限公司 | Method for preparing glycolide in batches |
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| CN111087381A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Refining treatment method of glycolide |
| CN111087381B (en) * | 2018-10-23 | 2021-03-26 | 中国石油化工股份有限公司 | Refining treatment method of glycolide |
| CN114478468B (en) * | 2020-10-26 | 2023-08-08 | 中国石油化工股份有限公司 | Method for refining glycolide and glycolide obtained by same |
| EP4234543A4 (en) * | 2020-10-26 | 2024-04-10 | China Petroleum & Chem Corp | Method for refining glycolide and glycolide obtained using same |
| 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 |
| CN114478468A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Method for refining glycolide and glycolide obtained by method |
| CN114790188A (en) * | 2021-01-26 | 2022-07-26 | 惠生工程（中国）有限公司 | Refining and purifying method of crude glycolide |
| CN115246812A (en) * | 2021-04-28 | 2022-10-28 | 上海浦景化工技术股份有限公司 | Method for refining glycolide |
| CN115246811A (en) * | 2021-04-28 | 2022-10-28 | 上海浦景化工技术股份有限公司 | Continuous production method of purified glycolide |
| CN115504957A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Glycolide refining method and glycolide obtained by same |
| 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 |
| 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 |
| CN114014835A (en) * | 2021-12-09 | 2022-02-08 | 内蒙古久泰新材料有限公司 | Glycolide purification process |
| CN116283888A (en) * | 2022-08-30 | 2023-06-23 | 深圳市迈启生物材料有限公司 | Method for preparing glycolide in batches |
| 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 |
| CN116283888B (en) * | 2022-08-30 | 2024-01-30 | 深圳市迈启生物材料有限公司 | Method for preparing glycolide in batches |
| 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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