阅读说明：本技术 一种高纯度乙交酯的制备方法 (A kind of preparation method of high-purity glycolide ) 是由 赵春华 苏红清 袁文博 陈儒浩 李建 于 2019-06-12 设计创作，主要内容包括：本发明提供了一种高纯度乙交酯的制备方法,采用减压脱水制得聚乙交酯(PGA)低聚物,再进行高温裂解蒸馏出粗品乙交酯,最后进行提纯得聚合级高纯度乙交酯,反应所需条件比较低,反应速度快,反应时间短,提纯后的乙交酯纯度高,能够满足聚合成高分子量聚乙交酯的需求。(The present invention provides a kind of preparation methods of high-purity glycolide, polyglycolide (PGA) oligomer is made using decompression dehydration, Pintsch process is carried out again distills out crude product glycolide, it finally carries out purifying to obtain polymerization grade high-purity glycolide, condition needed for reacting is relatively low, and reaction speed is fast, and the reaction time is short, glycolide purity is high after purification, can satisfy the demand for aggregating into high molecular weight polyglycolide.)

1. a kind of preparation method of high-purity glycolide (GA), includes the following steps:

Step 1: hydroxyacetic acid is dehydrated under reduced pressure；

Step 2: being warming up to certain temperature, decompression dehydration generates oligomeric hydroxy acetic acid under the action of catalyst；

Step 3: and then Pintsch process is carried out under high temperature, high vacuum condition；Through cooling collection system distillation, the friendship of crude product second is steamed Ester, then to the dissolution of thick glycolide, suction filtration, recrystallization, vacuum drying, obtain high-purity glycolide product.

2. preparation method according to claim 1, it is characterised in that: the catalyst is tin, magnesium, aluminium, antimony or titanium One of acylate, inorganic acid salt, metal oxide or alkyl metal cpd of category.

3. preparation method according to claim 2, it is characterised in that: the catalyst is zinc oxide, aluminium oxide, three oxygen Change one of two antimony, stannous octoate, zinc lactate or zinc acetate.

4. preparation method according to claim 1, it is characterised in that: the mass ratio of the hydroxyacetic acid and catalyst is 100~1000:1.

5. the preparation method according to claim 4, it is characterised in that: the mass ratio of the hydroxyacetic acid and catalyst is 120~600:1.

6. preparation method according to claim 1, it is characterised in that: the decompression dehydration time described in step 1 is 1~4h.

7. preparation method according to claim 6, it is characterised in that: the decompression dehydration time described in step 1 is 2~3h.

8. preparation method according to claim 1, it is characterised in that: decompression dehydration pressure described in step 1 be 0.04~ 0.06MPa。

9. preparation method according to claim 8, it is characterised in that: decompression dehydration pressure described in step 1 be 0.05~ 0.06MPa。

10. preparation method according to claim 1, it is characterised in that: decompression dehydration described in step 2 generates oligomeric hydroxy The acetic acidreaction time is 2~18 hours.

11. preparation method according to claim 10, it is characterised in that: decompression dehydration described in step 2 generates oligomeric hydroxyl The guanidine-acetic acid reaction time is 3~15 hours.

12. preparation method according to claim 1, it is characterised in that: decompression dehydration described in step 2 generates oligomeric hydroxy Acetic acid pressure is 0.06~0.09MPa.

13. preparation method according to claim 12, it is characterised in that: decompression dehydration described in step 2 generates oligomeric hydroxyl Guanidine-acetic acid pressure is 0.08~0.09MPa.

14. preparation method according to claim 1, it is characterised in that: the Pintsch process reaction temperature be 100~ 300℃。

15. preparation method according to claim 14, it is characterised in that: the Pintsch process reaction temperature be 110~ 290℃。

16. preparation method according to claim 1, it is characterised in that: distillation pressure described in step 3 be 1500Pa~ 0.1MPa。

17. preparation method according to claim 16, it is characterised in that: distillation pressure described in step 3 be 1000Pa~ 0.1MPa。

18. preparation method according to claim 1, it is characterised in that: the cooling collection system is multistage cooling receipts Collecting system.

19. preparation method according to claim 18, it is characterised in that: the cooling collection system, which is that three-level is cooling, to be received Collecting system.

20. preparation method according to claim 1, it is characterised in that: the solvent that the thick glycolide dissolution uses is first One of alcohol, dehydrated alcohol, ethyl acetate, acetone or butanone；Solvent usage is 0.5~2 times of crude product quality, refines number It is 3~5 times.

Technical field

The present invention relates to a kind of preparation methods of high-purity glycolide, belong to organic polymer technical field.

Background technique

Polyglycolide (PGA) is a kind of biodegradated polymer materal, nontoxic, nonirritant, has excellent biology Compatibility, biodegradable, absorption, intensity is high, plasticity is good, easy processing molding.Polyglycolide and poly- second third in recent years Lactide copolymers are used widely in the biological medicines Material Field such as operation suture thread, medicine controlled releasing, artificial organ.

Currently, the method for synthesis polyglycolide mainly has direct polycondensation method and glycolide ring-opening polymerisation method, direct polycondensation method It is that generally can only obtain relative molecular weight using the polycondensation of hydroxyacetic acid Direct Dehydration tens to thousands of oligomer, be difficult full The service performance of sufficient material；And use hydroxyacetic acid cyclic dimer -- glycolide ring-opening polymerisation can obtain high molecular weight Polyglycolic acid.In ring-opening polymerisation, the purity of lactide is to determine the most important factor of polymer molecular weight, to obtain macromolecule The polymer of amount, it is necessary to select the lactide of high-purity as raw material.

Usual glycolide is to use the polyglycolic acid of low molecular weight as intermediate, is closed by the method for Pintsch process At, with the method synthesize glycolide contain the impurity such as water, hydroxyacetic acid and glycolic acid oligomers, purity is not high, need it is more Secondary purification, this just makes the low yield of lactide, at high cost.

Summary of the invention

In order to solve the deficiencies in the prior art, the present invention provides a kind of preparation of high-purity glycolide (GA) and purification sides Method, this method is easy to operate, and reaction rate is fast, shortens the time for preparing glycolide, improves the yield of glycolide, reduces The preparation cost of glycolide.

The present invention is achieved through the following technical solutions: the present invention provides a kind of preparations of high-purity glycolide (GA) Method includes the following steps:

Step 1: hydroxyacetic acid is dehydrated under reduced pressure, is warming up to certain temperature, and then decompression dehydration generates under the action of catalyst Oligomeric hydroxy acetic acid；

Step 2: and then Pintsch process is carried out under high temperature, high vacuum condition；

Step 3: through cooling collection system distillation, steaming crude product glycolide, then to the dissolution of thick glycolide, suction filtration, recrystallization, vacuum It is dry, obtain high-purity glycolide product.

Preferably, the catalyst is acylate, inorganic acid salt, the metal oxidation of tin, magnesium, aluminium, antimony or titanium One of object or alkyl metal cpd.

It is furthermore preferred that the catalyst is zinc oxide, aluminium oxide, antimony oxide, stannous octoate, zinc lactate or acetic acid One of zinc.

Preferably, the mass ratio of the hydroxyacetic acid and catalyst is 100~1000:1.

It is furthermore preferred that the mass ratio of the hydroxyacetic acid and catalyst is 120~600:1.

Preferably, the decompression dehydration time described in step 1 is 1~4h.

It is furthermore preferred that the decompression dehydration time described in step 1 is 2~3h.

Preferably, decompression dehydration pressure described in step 1 is 0.04~0.06MPa.

It is furthermore preferred that decompression dehydration pressure described in step 1 is 0.05~0.06MPa.

Preferably, the generation oligomeric hydroxy acetic acidreaction time of decompression dehydration described in step 2 is 2~18 hours.

It is furthermore preferred that it is 3~15 hours that decompression dehydration described in step 2, which generates the oligomeric hydroxy acetic acidreaction time,.

Preferably, it is 0.06~0.09MPa that decompression dehydration described in step 2, which generates oligomeric hydroxy acetic acid pressure,.

It is furthermore preferred that it is 0.08~0.09MPa that decompression dehydration described in step 2, which generates oligomeric hydroxy acetic acid pressure,.

Preferably, the Pintsch process reaction temperature is 100~300 DEG C.

It is furthermore preferred that the Pintsch process reaction temperature is 110~290 DEG C.

Preferably, distillation pressure described in step 3 is 1500Pa~0.1MPa.

It is furthermore preferred that distillation pressure described in step 3 is 1000Pa~0.1MPa.

Preferably, the cooling collection system is multistage cooling collection system.

It is furthermore preferred that the cooling collection system is the cooling collection system of three-level.

Preferably, the solvent that the thick glycolide dissolution uses is methanol, dehydrated alcohol, ethyl acetate, acetone or butanone One of；Solvent usage is 0.5~2 north of crude product quality, and purification number is 3~5 times.

Compared with prior art, the beneficial effects of the present invention are:

Catalyst system of the present invention is efficient catalytic system, and prepolymer cracking process implements high temperature, condition of high vacuum degree, reaction Time is short, and by-product is few.

The system for collecting crude product is the cooling collection system of three-level, and crude product yield is up to 90% or more.

Crude product is filtered, repeatedly purification, glycolide purity may be up to 99.8% for the methods of recrystallization, product yield > 75%。

Specific embodiment

Below by specific embodiment, the invention will be further described, but not limited to this.