CN105566615A - Method for reducing yellowness index of polyglycolic acid - Google Patents
Method for reducing yellowness index of polyglycolic acid Download PDFInfo
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- CN105566615A CN105566615A CN201610023797.6A CN201610023797A CN105566615A CN 105566615 A CN105566615 A CN 105566615A CN 201610023797 A CN201610023797 A CN 201610023797A CN 105566615 A CN105566615 A CN 105566615A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for preparing polyglycolic acid. The yellowness index of polyglycolic acid is very low, and even when the polymerization temperature is high, the yellowness index of the product is also low. A catalyst is a composite catalyst, and the main component of the composite catalyst is a mixture of a traditional metal catalyst and an additive of an equal amount of substance. Compared with a single metal catalyst system, the catalytic activity of the composite catalyst is greatly improved. The polymerization reaction time is shortened to be within 20 min, and thus the polyglycolic acid production efficiency is greatly improved. The yellowness index of polyglycolic acid prepared through the method is low.
Description
Technical field
The present invention relates to a kind of manufacture method of polyglycolic acid.Described method is add additive in the metal catalyst of catalysis glycollide ring-opening polymerization, effectively reduces the yellowness index of product.
Background technology
In several centuries in the past, processing a large amount of rubbish is one of serious problems of facing of the whole world.Such as, the annual output 3000kg rubbish of each family of the U.S., these rubbish must be dealt carefully with.Degradation material can play a significant role in treating refuse (reference 1).
Polyglycolic acid (PGA) is a kind of degradable aliphatic polyester, and its research and development has carried out decades, and it is mainly used in medical field (reference 2 ~ 4).In addition, it is acknowledged as the polymkeric substance (reference 5,6) being applicable to being applied to following wrapping material.PGA has good mechanical property, can mention in the same breath with present standard packaging material polystyrene.
Preparation PGA mainly contains two operational paths: the polycondensation of (1) lactic acid; (2) glycollide ring-opening polymerization.There is two problems in polycondensation operational path: (1) is difficult to the polymkeric substance preparing high molecular; (2) unreacted monomer is remained in polymkeric substance.Ring-opening polymerization technique can synthesize the polymkeric substance of high molecular and monomer conversion is very high.Its shortcoming is that production process step is many, and abstraction and purification high cost, adds the production cost of product.The PGA of high molecular is generally prepared by the ring-opening polymerization of glycollide.
In coal-ethylene glycol rapid scale advances, the bottleneck of correlation technique development will be become to the exploitation of by product (such as dimethyl oxalate).The present invention uses the hydrogenation products methyl glycolate of dimethyl oxalate to be raw material, and polycondensation synthesis lower molecular weight PGA, glycollide is prepared in further depolymerization, obtains the PGA (reference 7) of high molecular eventually through glycollide ring-opening polymerization.
Document 8 reports and uses SnCl
2﹒ 2H
2the Study of optimization of O catalysis glycollide polymerization, the polyglycolic acid yellowness index prepared by this method is bigger than normal, which has limited the range of application of polyglycolic acid.
Document 9 reports the color improving polymerisate by reducing polymerization temperature.Although this method reduces the yellowness index of product, because polymerization temperature reduces, polymerization time extends greatly, and production efficiency reduces greatly.
The present invention reports in ring opening polymerisation process, the amount of substance additive such as to add to metal catalyst, and this is conducive to the yellowness index reducing PGA, compensate for the deficiency of document 8 and document 9 methods involving.Technology provided by the invention also can be used for synthesizing other aliphatic polyester.
Reference
Document 1:SJacobsena, HGFritza, PhDegeeb, PhDuboisb, RJeromeb.Single-stepreactiveextrusionofPLLAinacorotating twin-screwextruderpromotedby2-ethylhexanoicacidtin (II) saltandtriphenylphosphine [J] .Polymer, 2000,41:3395 ~ 3403
Document 2:HRKricheldorf, IKreiserSaunders, CJ ü rgens, DWolter.Polylactides-synthesis, characterizationandmedicalapplication [J] .MacromolecularSymposia, 1996,103 (1): 85 ~ 102
Document 3:NieuwenhuisJ, MolAC.Methodforthepreparationofapolymerlactide [J] .EP314245,1989-05-03
Document 4:BEling, SGogolewski, AJPennings.Biodegradablematerialsofpoly (l-lacticacid): 1.Melt-spunandsolution-spunfibres [J] .Polymer, 1982,23:1587 ~ 1593
Document 5:SinclairRG.TheCaseforPolylacticAcidasaCommodityPackagi ngPlastic [J] .JournalofMacromolecularSciencePartAPure & AppliedChemistry, 1996,33 (5): 585 ~ 597
Document 6:GruberPR, KolstadES, IwenML, BensonRD, BorchartRL.Continuousprocessforthemanufactureoflactidean dlactidepolymers [P] .WO9315127,1993-08-05
Document 7: Chen Qun, Xu Ping, Cui Aijun. coal-based polyglycolic acid technical progress [J]. chemical industry is in progress, and 2011,30 (1): 172 ~ 180
Document 8: Chen Qun, Cui Aijun, He Mingyang, Zhou Weiyou. method [J] .CN103304786, the 2013-9-18 of polyhydroxy acid with high molecular weight are prepared in a kind of serialization
Document 9:YukichikaKawakami, NobuoSato, MitsuruHoshino, ToshitakaKouyama, ZenyaShiika.Orientedpolyglycolicacidfilmandproductionpro cessthereof [P] .US5853639,1998-12-29
Summary of the invention
In recent years, in the plastics comprising polymeric film, along with the change of human consumer's hobby, non-coloring or the light commodity of color become main flow.If with current polyglycolic acid for raw material, yellow painted grow, thus cause the problem that sometimes cannot obtain desired color product.Polyglycolic acid is heated and easily manifests yellow, and such as, when synthesizing polyglycolic acid, at high temperature carry out heated polymerizable for the consideration of production efficiency aspect, now this color development problem obviously shows.Although production efficiency is higher under high temperature, in order to make product not manifest yellow, have to avoid high temperature.For this reason, need a kind ofly to suppress glycollide to be heated in ring opening polymerisation process to manifest yellow inhibitor.
In addition, the method turned yellow after being heated as suppressing polymkeric substance, it is also proposed the method for adding reductive agent when manufacturing polyglycolic acid in polymkeric substance.But, if add other compositions such as reductive agent, not only cause product cost to raise, sometimes also can cause the molecular weight degradation of polymkeric substance.
So the problem to be solved in the present invention is to provide a kind of manufacture method of polyglycolic acid.The yellowness index of this polyglycolic acid is very low, even if when glycollide is polymerized at relatively high temperatures, the color of product is also very low.
The present inventor has carried out conscientiously studying intensively to solve the problem.Result is noticed: in glycollide ring opening polymerisation process, and in traditional metal catalyst, the amount of substance additive such as to add, the catalytic activity of catalyzer improves greatly.Polymerization reaction time foreshortens to 20min, and polyglycolic acid yellowness index prepared by the method significantly reduces.
Method concrete steps provided by the invention are as follows:
(1) under anhydrous and oxygen-free condition, in atmosphere of inert gases, in reaction flask, glycollide, metal catalyst and additive is added.Use magnetic force heating stirrer reaction stirred, reactant is heated polymerizable in oil bath.
(2) reactant is polymerized for some time under assigned temperature.
(3), after being polymerized, reaction flask is broken into pieces taking-up product.
Wherein, described rare gas element is selected from the one in argon gas and nitrogen, preferred nitrogen.Be polymerized to mass polymerization.
Described catalyzer, comprising Sn powder and the compound containing Sn atom, Bi powder and the compound containing Bi atom, Sr powder and the compound containing Sr atom.The described compound containing Sn atom, comprising SnO, SnCl
2﹒ 2H
2the carboxylic acid compound of O and Sn.The carboxylic acid compound of described Sn, comprising Sn (Oct)
2deng the Sn carboxylate salt that carbon atom quantity scope is 1 ~ 30, preferred Sn (Oct)
2.
The described compound containing Bi atom, comprising Bi
2o
3, BiCl
3with the carboxylic acid compound of Bi.The carboxylic acid compound of described Bi, comprising Bi (OAc)
3deng the Bi carboxylate salt that carbon atom quantity scope is 1 ~ 30, preferred Bi (OAc)
3.
The described compound containing Sr atom, comprising SrO, SrCl
2with the carboxylic acid compound of Sr.The carboxylic acid compound of described Sr, comprising Sr (OAc)
2deng the Sr carboxylate salt that carbon atom quantity scope is 1 ~ 30, preferred Sr (OAc)
2.
Described additive, comprising Ph
3p, tosic acid and BF
3deng material, preferred Ph
3p.
Described heated polymerizable process, wherein polymerization temperatures range is 150 ~ 300 DEG C, and preferable range is 170 ~ 210 DEG C.Polymerization time scope is 1 ~ 180min, and preferable range is 15 ~ 60min.
Describedly add glycollide in reaction flask and catalyzer, wherein the add-on scope of metal catalyst is 10 ~ 100000ppm, and preferable range is 500 ~ 1000ppm.Described add additive in reaction flask and metal catalyst, wherein the amount of additive and metallic catalyst material is 0.5:1 ~ 10:1 than scope, preferred 1:1.
Add additive in polymerization reaction system after, the activity of catalystic converter system improves greatly.Add additive to be conducive to reaction and to carry out, reduce the requirement to polymerization temperature in ring-opening polymerization technique.Additive in the reaction existing certain katalysis has again certain antioxygenation, effectively can reduce the generation of side reaction, improve the color of PGA product.
Here is the present invention's measuring method used
(1) molecular weight (GPC)
First prepare the HFIP solution that trifluoroacetic acid sodium content is 5mmol/L, get a certain amount of non-crystalline state sample dissolution, be made into the solution that massfraction is 0.05 ~ 0.3%.Teflon membrane filter through 0.4 μm of aperture filters, and gets 20 μ L and joins in Shimadzu (Japan) system " LC-20ADGPC " sampler, by calculating weight-average molecular weight and molecular weight distribution.
Test condition: column temperature 40 DEG C; Elutriant: the hexafluoroisopropanol being dissolved with 5mmol/L sodium trifluoroacetate; Flow velocity 1mL/min; Detector: RI detector; Correct: use molecular weight to gather methyl e pioic acid methyl ester in 5 kinds of different standardss that 7000 to 200000 do not wait and carry out molecular weight calibration.
(2) monomer conversion
By about 300mg sample in the dimethyl sulfoxide (DMSO) (DMSO) of about 6g, at 150 DEG C, heat about 10 minutes, dissolve, be cooled to room temperature, then filter.A certain amount of internal standard substance 4-chlorobenzophenone and acetone is added in this filtrate.Measure 2 these solution of μ L, be injected in GC device, measure.The numerical value obtained by this mensuration, with the form of the mass percent contained in polymkeric substance, calculates residual monomers amount, converts monomer conversion to.
(3) yellowness index
U.S. HunterLabScanXE yellowness index instrument is adopted to measure.
Measuring method
1. use Universalpulverizer by powdered for PGA sample comminution.
2. rectify an instrument
Rectify an instrument, to correcting successfully by instrument prompting priority black glass plate, white correcting plate.
3. sample is tested
Application of sample, to sample cup, covers light shield.
4. hit testing sample button starts test sample
To be tested complete, repeated sampling product are tested, and measure and average for three times, record data.
Embodiment
The present invention is described further with reference to following examples, but these embodiments sheerly illustration of the present invention.
Embodiment 1
In single port flask, add 10g glycollide under nitrogen protection, use micro-sampling pin in reaction flask, inject 4.02 μ LSn (Oct)
2.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 60min at being aggregated in 170 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 2
10g glycollide and 0.00325gPh is added under nitrogen protection in single port flask
3p, uses micro-sampling pin in reaction flask, inject 4.00 μ LSn (Oct)
2.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 60min at being aggregated in 170 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 3
10g glycollide and 0.00512gSnO is added under nitrogen protection in single port flask.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 40min at being aggregated in 200 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 4
10g glycollide is added, 0.00509gSnO and 0.00328gPh under nitrogen protection in single port flask
3p.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 40min at being aggregated in 200 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 5
10g glycollide and 0.01089gSnCl is added under nitrogen protection in single port flask
2﹒ 2H
2o.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 15min at being aggregated in 210 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 6
10g glycollide is added, 0.01291gSnCl under nitrogen protection in single port flask
2﹒ 2H
2o and 0.01159gPh
3p.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 15min at being aggregated in 210 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 7
10g glycollide and 0.00516gBi (OAc) is added under nitrogen protection in single port flask
3.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 60min at being aggregated in 170 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 8
10g glycollide is added under nitrogen protection, 0.00526gBi (OAc) in single port flask
3and 0.00324gPh
3p.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 60min at being aggregated in 170 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 9
10g glycollide and 0.00531gBi is added under nitrogen protection in single port flask
2o
3.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 40min at being aggregated in 200 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 10
10g glycollide is added, 0.00596gBi under nitrogen protection in single port flask
2o
3and 0.00391gPh
3p.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 40min at being aggregated in 200 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 11
10g glycollide and 0.01209gBiCl is added under nitrogen protection in single port flask
3.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 15min at being aggregated in 210 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 12
10g glycollide is added, 0.01278gBiCl under nitrogen protection in single port flask
3and 0.01186gPh
3p.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 15min at being aggregated in 210 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 13
10g glycollide and 0.00572gSr (OAc) is added under nitrogen protection in single port flask
2.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 60min at being aggregated in 170 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 14
10g glycollide is added under nitrogen protection, 0.00569gSr (OAc) in single port flask
2and 0.00326gPh
3p.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 60min at being aggregated in 170 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 15
10g glycollide and 0.00552gSrO is added under nitrogen protection in single port flask.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 40min at being aggregated in 200 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 16
10g glycollide is added, 0.00561gSrO and 0.00319gPh under nitrogen protection in single port flask
3p.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 40min at being aggregated in 200 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 17
10g glycollide and 0.01099gSrCl is added under nitrogen protection in single port flask
2.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 15min at being aggregated in 210 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
Embodiment 18
10g glycollide is added, 0.01288gSrCl under nitrogen protection in single port flask
2and 0.01182gPh
3p.Use magnetic stirrer monomer and catalyzer, reactant is heated polymerizable in oil bath, carries out 15min at being aggregated in 210 DEG C.After being polymerized, reaction flask is broken into pieces taking-up product.Measure the molecular weight of polymkeric substance afterwards, monomer conversion and yellowness index, correlated results is in table 1.
The PGA performance characterization of the various catalyst preparing of table 1
Claims (10)
1. reduce a method for polyglycolic acid yellowness index, the concrete steps of the method are as follows:
(1) under anhydrous and oxygen-free condition, in atmosphere of inert gases, in reaction flask, glycollide, metal catalyst and additive is added.Use magnetic force heating stirrer reaction stirred, reactant is heated polymerizable in oil bath.
(2) reactant is polymerized for some time under assigned temperature.
(3), after being polymerized, reaction flask is broken into pieces taking-up product.
2. method according to claim 1, is characterized in that, described rare gas element is selected from the one in argon gas and nitrogen, preferred nitrogen.Be polymerized to mass polymerization.
3. catalyzer according to claim 1, comprising Sn powder and the compound containing Sn atom, Bi powder and the compound containing Bi atom, Sr powder and the compound containing Sr atom.
4. the compound containing Sn atom according to claim 4, comprising SnO, SnCl
2﹒ 2H
2the carboxylic acid compound of O and Sn.The carboxylic acid compound of described Sn, comprising Sn (Oct)
2deng the Sn carboxylate salt that carbon atom quantity scope is 1 ~ 30, preferred Sn (Oct)
2.
5. the compound containing Bi atom according to claim 4, comprising Bi
2o
3, BiCl
3with the carboxylic acid compound of Bi.The carboxylic acid compound of described Bi, comprising Bi (OAc)
3deng the Bi carboxylate salt that carbon atom quantity scope is 1 ~ 30, preferred Bi (OAc)
3.
6. the compound containing Sr atom according to claim 4, comprising SrO, SrCl
2with the carboxylic acid compound of Sr.The carboxylic acid compound of described Sr, comprising Sr (OAc)
2deng the Sr carboxylate salt that carbon atom quantity scope is 1 ~ 30, preferred Sr (OAc)
2.
7. additive according to claim 1, comprising Ph
3p, tosic acid and BF
3deng material, preferred Ph
3p.
8. heated polymerizable process according to claim 1, wherein polymerization temperatures range is 150 ~ 300 DEG C, and preferable range is 170 ~ 210 DEG C.Polymerization time scope is 1 ~ 180min, and preferable range is 15 ~ 60min.
9. add the glycollide in reaction flask and catalyzer according to claim 1, wherein the add-on scope of metal catalyst is 10 ~ 100000ppm, and preferable range is 500 ~ 1000ppm.
10. according to claim 1ly add additive in reaction flask and metal catalyst, wherein the amount of additive and metallic catalyst material is 0.5:1 ~ 10:1 than scope, preferred 1:1.
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Cited By (3)
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|---|---|---|---|---|
| CN105885025A (en) * | 2016-05-26 | 2016-08-24 | 常州大学 | High-efficiency catalyst for synthesizing polylactic acid |
| CN105906789A (en) * | 2016-05-26 | 2016-08-31 | 常州大学 | High-efficiency catalyst for synthesizing polyglycollic acid |
| EP3736303A1 (en) | 2019-05-06 | 2020-11-11 | Evonik Operations GmbH | Novel catalyzed synthesis of biodegradable polyesters |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885025A (en) * | 2016-05-26 | 2016-08-24 | 常州大学 | High-efficiency catalyst for synthesizing polylactic acid |
| CN105906789A (en) * | 2016-05-26 | 2016-08-31 | 常州大学 | High-efficiency catalyst for synthesizing polyglycollic acid |
| EP3736303A1 (en) | 2019-05-06 | 2020-11-11 | Evonik Operations GmbH | Novel catalyzed synthesis of biodegradable polyesters |
| WO2020225044A1 (en) | 2019-05-06 | 2020-11-12 | Evonik Operations Gmbh | Novel catalyzed synthesis of biodegradable polyesters |
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