CN111087580A - Method for preparing polyglycolic acid - Google Patents
Method for preparing polyglycolic acid Download PDFInfo
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- CN111087580A CN111087580A CN201811235288.5A CN201811235288A CN111087580A CN 111087580 A CN111087580 A CN 111087580A CN 201811235288 A CN201811235288 A CN 201811235288A CN 111087580 A CN111087580 A CN 111087580A
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- polyglycolic acid
- molecular weight
- reaction
- polycondensation reaction
- glycolic acid
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 69
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 36
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 16
- -1 glycolic acid ester Chemical class 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 10
- 150000004820 halides Chemical class 0.000 claims description 10
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- ATLXDVFEVUTEMF-UHFFFAOYSA-N n,n'-dicyclopentylmethanediimine Chemical compound C1CCCC1N=C=NC1CCCC1 ATLXDVFEVUTEMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000005227 gel permeation chromatography Methods 0.000 description 21
- 238000009826 distribution Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 206010000050 Abdominal adhesions Diseases 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 206010014561 Emphysema Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000012752 Hepatectomy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229940109239 creatinine Drugs 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003180 well treatment fluid Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- 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 relates to a preparation method of polyglycolic acid, which mainly solves the problem that the glycolic acid polycondensation reaction can not obtain the weight-average molecular weight MwGreater than 2 million polymers. By using a process for the preparation of polyglycolic acid comprising reacting glycolic acid or glycolic acid ester to obtain a weight average molecular weight MwThe above-mentioned problems are solved preferably by a process 1 of polyglycolic acid having a weight average molecular weight of less than 20000 and a process 2 of adding a dehydrating agent to the obtained polyglycolic acid and polymerizing the mixture with a dehydrating agent.
Description
Technical Field
The invention relates to a preparation method of polyglycolic acid.
Background
Polyglycolic acid (also known as polyglycolic acid (PGA)) is a biodegradable aliphatic polymer, which is hydrolyzed under the catalysis of enzymes or acids and bases in microorganisms or organisms to finally form carbon dioxide and water, and has been widely used in the medical field due to its excellent biocompatibility. Polyglycolic acid can be used for preparing absorbable surgical suture, protective sleeve after cutting emphysema, tissue engineering material, ligation band in hepatectomy, isolation mesh for preventing postoperative intestinal adhesion, material for promoting cell attachment, orthopedic material, etc. In addition, polyglycolic acid resin is also used for a well treatment fluid in oil production because of its small environmental load. Since films made of polyglycolic acid are also excellent in gas barrier properties, polyglycolic acid is expected to be used as agricultural materials or materials for various packages (containers). At present, the most important application of polyglycolic acid is as a surgical suture.
There are two routes to the preparation of polyglycolic acid, one is obtained by direct esterification polycondensation of glycolic acid, also known as one-step process. The polyglycolic acid obtained by this method has a low molecular weight, usually MwLess than 2 ten thousand, the melt strength is not enough during molding and processing, and the melt cannot be used for subsequent application; another method is to dehydrate and condense glycolic acid to obtain a polymer with relatively low molecular weight, then to heat and decompose polyglycolic acid to obtain six-membered cyclic glycolide formed by dehydrating two molecules of glycolic acid, and to obtain polyglycolic acid with molecular weight more than 10 ten thousand by ring-opening polymerization of glycolide, which is also called a two-step method. Polyglycolic acid used in surgical sutures places high demands on the molecular weight and melt strength of the polymer, and the inherent viscosity of polyglycolic acid suitable for melt extrusion and preparation of absorbable surgical sutures is generally greater than 1.0 dL/g. Polyglycolic acid, which meets this viscosity requirement, is typically prepared in a two-step process.
Patent CN101616907A reports a method for preparing glycolide by using glycolic acid and a method for preparing a weight average molecular weight M by using ring-opening polymerization of glycolidewA process for polyglycolic acid of greater than 20 million. The polyglycolic acid is prepared by the two-step method, the process is more complicated than the one-step method, a large amount of high-boiling point solvent is used in the polymerization process, the energy consumption of the preparation process is increased, and simultaneously, higher requirements on the recycling of the solvent are provided.
Patent CN102295765B reports that a copolymer having a molecular weight of 1.8 to 17.7 ten thousand is obtained by solid phase copolymerization of glycolic acid and lactic acid using biomass creatinine as a catalyst, but the reaction time of the solid phase polymerization is 96 hours or more, and the reaction time is long. In addition, there is no report that this method is used for the preparation of polyglycolic acid.
Patent CN107177032A (plausibility chemical) reports a method for directly preparing high molecular weight polyglycolic acid from glycolic acid or methyl glycolate. The method comprises the following steps: (1) carrying out pre-polycondensation reaction on monomer glycolic acid or methyl glycolate under the action of a catalyst to prepare glycolic acid or methyl glycolate prepolymer of 0.3-0.7 dl/g; (2) pulverizing the glycolic acid or methyl glycolate prepolymer obtained in the step (1) to 10-300 mesh with a pulverizer to obtain glycolic acid or methyl glycolate prepolymer powder; (3) feeding the glycolic acid or methyl glycolate prepolymer powder obtained in step (2) to a fluidized bed dryer, and performing solid phase polycondensation to obtain polyglycolic acid having an intrinsic viscosity of 1.0dl/g or more. In this process, the solid phase polycondensation reaction is carried out in a fluidized bed, and the reaction time is usually 72 hours or more, which is relatively long.
Disclosure of Invention
The technical problem to be solved by the invention is that the weight average molecular weight M is difficult to obtain by glycolic acid polycondensation in the prior artwMore than 2 ten thousand of polyglycolic acid, and provides a method for preparing polyglycolic acid, which has the advantages of one-step preparation of polyglycolic acid, great increase of molecular weight of the obtained polyglycolic acid, great reduction of reaction time and obvious reduction of energy consumption.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for the preparation of polyglycolic acid comprising reacting glycolic acid or glycolate to obtain a mixture containing a weight average molecular weight MwA step 1 of reacting polyglycolic acid of less than 20000, and a step 2 of adding a dehydrating agent to the obtained reaction product to further polymerize.
In the above technical scheme, the dehydrating agent used is preferably one or a combination of more of dicyclohexylcarbodiimide, dicyclopentylcarbodiimide, N' -diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
In the technical scheme, the dosage of the dehydrating agent is 0.5-2% of the mass of the glycolic acid or the glycolate.
In the above technical scheme, the reaction in step 1 preferably comprises an atmospheric polycondensation reaction and a reduced-pressure polycondensation reaction of glycolic acid or glycolate in the presence of a catalyst.
In the above technical scheme, the catalyst used is preferably tin oxide, halide or organic acid salt, or antimony oxide, halide or organic acid salt, or zinc oxide, halide or organic acid salt, or aluminum oxide, halide or organic acid salt, or a composite catalyst of two or more of the above; further preferably an oxide, halide or organic acid salt of tin; more preferably an organic acid salt of tin.
In the technical scheme, the dosage of the catalyst is preferably 0.001-1 wt% of the mass of the glycolic acid or the glycolate.
In the technical scheme, the normal-pressure polycondensation reaction temperature is preferably 110-220 ℃.
In the technical scheme, the vacuum degree of the reduced pressure polycondensation reaction is preferably 100-10000 Pa; the preferable temperature of the reduced pressure polycondensation is 160-240 ℃.
In the above technical solution, the polymerization in the step 2 is preferably a polycondensation reaction.
In the technical scheme, the temperature of the polycondensation reaction in the step 2 is preferably 200-220 ℃; the time of the polycondensation reaction is preferably 6-8 h.
In the above technical scheme, the weight average molecular weight M of the reactant obtained in the step 1wPreferably not less than 10000.
The inventor surprisingly found that the weight average molecular weight of polyglycolic acid is greatly improved by controlling the polymerization process and the method of adding the dehydrating agent, and the polyglycolic acid with the weight average molecular weight of more than 5 ten thousand and the intrinsic viscosity of more than 1.0dl/g can be prepared by a one-step method.
By adopting the technical scheme of the invention, polyglycolic acid with the weight-average molecular weight of more than 5 ten thousand and the intrinsic viscosity of more than 1.0dl/g can be prepared by a one-step method, compared with the traditional one-step method for preparing polyglycolic acid, the molecular weight of the polyglycolic acid prepared by the technical scheme of the invention is greatly improved, compared with the method for preparing polyglycolic acid by solid phase polycondensation reported by other patents, the method used by the invention has the advantages of greatly shortening the reaction time, obviously reducing the energy consumption and obtaining better technical effect.
The invention is further illustrated by the following specific examples.
Detailed Description
The present invention adopts the following methods to characterize polyglycolic acid obtained by polymerization.
Gel Permeation Chromatography (GPC): the mobile phase was concentrated at 5mmol.L by gel permeation chromatography model PL50 from Agilent-1The weight average molecular weight and the molecular weight distribution coefficient of the polymer were measured using a polymethyl methacrylate standard sample of a known molecular weight as a reference.
The intrinsic viscosity ([ η ]) was measured in a constant-temperature water bath at (25. + -. 0.1) ° C using a Ubbelohde viscometer with phenol/1, 1,2, 2-tetrachloroethane (m: 1) as a solvent.
[ example 1 ]
1200g of glycolic acid crystals and 2.0g of stannous octoate were added to a 5L reactor, heated to 90 ℃ under normal pressure to completely melt the reactants, after which the system was warmed from 90 ℃ to 200 ℃ over 2h and reacted at this temperature for 2h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing to react for 2h to obtain polyglycolic acid. The weight-average molecular weight M was determined by GPCw14000, a molecular weight distribution coefficient PDI of 2.06, and an intrinsic viscosity of 0.33 dl/g.
Adding 20g of N, N' -dicyclohexylcarbodiimide into the reaction kettle, heating to 210 ℃, vacuumizing until the system pressure is 1000pa, and continuously reacting for 10h to obtain 907g of polyglycolic acid solid. The weight-average molecular weight M was determined by GPCw79300, the molecular weight distribution coefficient PDI was 1.91, and the intrinsic viscosity was 1.10 dl/g.
[ example 2 ]
2000g of a 60% strength aqueous glycolic acid solution and 2.0g of stannous octoate were placed in a 5L reactor, heated to 140 ℃ under normal pressure and reacted at this temperature for 1 hour, and water was distilled off. The system was then warmed from 140 ℃ to 200 ℃ over 2h and reacted at this temperature for 1h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing to react for 2h to obtain polyglycolic acid. The weight-average molecular weight M was determined by GPCw13200, a molecular weight distribution coefficient PDI of 1.99 and an intrinsic viscosity of 0.31 dl-g。
Adding 20g of N, N' -dicyclohexylcarbodiimide into the reaction kettle, heating to 210 ℃, vacuumizing until the system pressure is 1000pa, and continuously reacting for 10h to obtain 900g of solid polyglycolic acid. The weight-average molecular weight M was determined by GPCw78500, the molecular weight distribution coefficient PDI was 1.87, and the intrinsic viscosity was 1.02 dl/g.
[ example 3 ]
1200g of glycolic acid crystals and 2.0g of stannous octoate were added to a 5L reactor, heated to 90 ℃ under normal pressure to completely melt the reactants, after which the system was warmed from 90 ℃ to 200 ℃ over 2h and reacted at this temperature for 2h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing to react for 2h to obtain polyglycolic acid. The weight-average molecular weight M was determined by GPCw14000, a molecular weight distribution coefficient PDI of 2.06, and an intrinsic viscosity of 0.33 dl/g.
20g of N, N' -diisopropylcarbodiimide was added into the reaction kettle, the temperature was raised to 210 ℃, vacuum was applied until the system pressure was 1000pa, and the reaction was continued for 10 hours to obtain 899g of polyglycolic acid solid. The weight-average molecular weight M was determined by GPCw77600, the molecular weight distribution coefficient PDI is 1.93, and its intrinsic viscosity is 1.00 dl/g.
[ example 4 ]
2000g of a 60% strength aqueous glycolic acid solution and 2.0g of stannous octoate were placed in a 5L reactor, heated to 140 ℃ under normal pressure and reacted at this temperature for 1 hour, and water was distilled off. The system was then warmed from 140 ℃ to 200 ℃ over 2h and reacted at this temperature for 1h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing to react for 2h to obtain polyglycolic acid. The weight-average molecular weight M was determined by GPCw13200, a molecular weight distribution coefficient PDI of 1.99, and an intrinsic viscosity of 0.31 dl/g.
20g of N, N' -diisopropylcarbodiimide is added into the reaction kettle, the temperature is raised to 210 ℃, the vacuum is pumped until the system pressure is 1000pa, and the reaction is continued for 10h to obtain 902g of solid polyglycolic acid. The weight-average molecular weight M was determined by GPCw78100, a molecular weight distribution coefficient PDI of 1.90, and an intrinsic viscosity of 1.02dl/g。
[ example 5 ]
1200g of glycolic acid crystals and 2.0g of stannous octoate were added to a 5L reactor, heated to 90 ℃ under normal pressure to completely melt the reactants, after which the system was warmed from 90 ℃ to 200 ℃ over 2h and reacted at this temperature for 2h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing to react for 2h to obtain polyglycolic acid. The weight-average molecular weight M was determined by GPCw14000, a molecular weight distribution coefficient PDI of 2.06, and an intrinsic viscosity of 0.33 dl/g.
Adding 20g of N, N' -dicyclopentylcarbodiimide into the reaction kettle, heating to 210 ℃, vacuumizing until the system pressure is 1000pa, and continuously reacting for 10h to obtain 894g of solid polyglycolic acid. The weight-average molecular weight M was determined by GPCw64100, the molecular weight distribution coefficient PDI was 2.02, and the intrinsic viscosity was 0.95 dl/g.
[ example 6 ]
2000g of a 60% strength aqueous glycolic acid solution and 2.0g of stannous octoate were placed in a 5L reactor, heated to 140 ℃ under normal pressure and reacted at this temperature for 1 hour, and water was distilled off. The system was then warmed from 140 ℃ to 200 ℃ over 2h and reacted at this temperature for 1h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing to react for 2h to obtain polyglycolic acid. The weight-average molecular weight M was determined by GPCwIt was 13600, had a molecular weight distribution coefficient PDI of 1.97 and an intrinsic viscosity of 0.32 dl/g.
Adding 20g of N, N' -dicyclopentylcarbodiimide into the reaction kettle, heating to 210 ℃, vacuumizing until the system pressure is 1000pa, and continuously reacting for 10h to obtain 886g of solid polyglycolic acid. The weight-average molecular weight M was determined by GPCw66500, the molecular weight distribution coefficient PDI is 1.98, and its intrinsic viscosity is 0.98 dl/g.
[ example 7 ]
1200g of glycolic acid crystals and 2.0g of stannous octoate are added into a 5L reaction kettle, the mixture is heated to 90 ℃ under normal pressure to completely melt the reactants, then the system is heated from 90 ℃ to 200 ℃ within 2h and reacted for 2h at the temperature, and during the period, the mixture is steamedThe water produced in the reaction is distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing to react for 2h to obtain polyglycolic acid. The weight-average molecular weight M was determined by GPCw14000, a molecular weight distribution coefficient PDI of 2.06, and an intrinsic viscosity of 0.33 dl/g.
20g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is added into a reaction kettle, the temperature is raised to 210 ℃, the vacuum is carried out until the system pressure is 1000pa, and the reaction is continued for 10h to obtain 901g of solid polyglycolic acid. The weight-average molecular weight M was determined by GPCw69200, the molecular weight distribution coefficient PDI was 1.93, and the intrinsic viscosity was 1.00 dl/g.
[ example 8 ]
2000g of a 60% strength aqueous glycolic acid solution and 2.0g of stannous octoate were placed in a 5L reactor, heated to 140 ℃ under normal pressure and reacted at this temperature for 1 hour, and water was distilled off. The system was then warmed from 140 ℃ to 200 ℃ over 2h and reacted at this temperature for 1h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing to react for 2h to obtain polyglycolic acid. The weight-average molecular weight M was determined by GPCwIt was 13600, had a molecular weight distribution coefficient PDI of 1.97 and an intrinsic viscosity of 0.32 dl/g.
Adding 20g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into the reaction kettle, heating to 210 ℃, vacuumizing until the system pressure is 1000pa, and continuously reacting for 10h to obtain 904g of solid polyglycolic acid. The weight-average molecular weight M was determined by GPCw70100, the molecular weight distribution coefficient PDI was 2.02, and the intrinsic viscosity was 0.99 dl/g.
[ COMPARATIVE EXAMPLE 1 ]
2000g of a 60% strength aqueous glycolic acid solution and 2.0g of stannous octoate were placed in a 5L reactor, heated to 140 ℃ under normal pressure and reacted at this temperature for 1 hour, and water was distilled off. The system was then warmed from 140 ℃ to 200 ℃ over 2h and reacted at this temperature for 1h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the pressure of the system is 5000Pa, and continuing the reaction for 2 h. Then, the reaction temperature was raised to 210 ℃ and vacuum was applied to 1000Pa, and the reaction was carried out under these conditions for 12 hours to obtain 903g of solid polyglycolic acid. The weight-average molecular weight Mw was 23700, the molecular weight distribution coefficient PDI was 2.33, and the intrinsic viscosity was 0.40dl/g as measured by GPC.
[ COMPARATIVE EXAMPLE 2 ]
1200g of glycolic acid crystals and 2.0g of stannous octoate were added to a 5L reactor, heated to 90 ℃ under normal pressure to completely melt the reactants, after which the system was warmed from 90 ℃ to 200 ℃ over 2h and reacted at this temperature for 2h, during which time the water formed in the reaction was distilled off. Then vacuumizing until the system pressure is 5000Pa, and continuing the reaction for 2 h. Then, the reaction temperature was raised to 210 ℃ and vacuum was applied to 1000Pa, and the reaction was carried out under these conditions for 24 hours to obtain 910g of solid polyglycolic acid. The weight-average molecular weight M was determined by GPCw25500, the molecular weight distribution coefficient PDI was 2.27, and the intrinsic viscosity was 0.45 dl/g.
Claims (10)
1. A process for the preparation of polyglycolic acid comprising reacting glycolic acid or glycolate to a monomer containing a weight average molecular weight MwA step 1 of reacting polyglycolic acid of less than 20000, and a step 2 of adding a dehydrating agent to the obtained reaction product to further polymerize.
2. A process for the preparation of polyglycolic acid according to claim 1, where said dehydrating agent is selected from one or a combination of several of dicyclohexylcarbodiimide, dicyclopentylcarbodiimide, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
3. The method for producing polyglycolic acid according to claim 1, wherein the amount of the dehydrating agent is 0.5 to 2% by mass based on glycolic acid or glycolate.
4. The process for producing polyglycolic acid according to claim 1, wherein the reaction in step 1 comprises an atmospheric pressure polycondensation reaction and a reduced pressure polycondensation reaction of glycolic acid or glycolate in the presence of a catalyst.
5. A process for producing polyglycolic acid according to claim 4, where the catalyst used is an oxide, halide or organic acid salt of tin, or an oxide, halide or organic acid salt of antimony, or an oxide, halide or organic acid salt of zinc, or an oxide, halide or organic acid salt of aluminum, or a composite catalyst of two or more of the foregoing; preferably tin oxide, halide or organic acid salt; more preferably an organic acid salt of tin.
6. A process for producing polyglycolic acid according to claim 4, wherein the amount of the catalyst is 0.001 to 1 wt% based on the mass of glycolic acid or glycolic acid ester.
7. A process for producing polyglycolic acid according to claim 4, wherein the normal pressure polycondensation reaction temperature is 110 to 220 ℃.
8. A process for producing polyglycolic acid according to claim 4, wherein the degree of vacuum of the reduced-pressure polycondensation reaction is 100 to 10000 Pa; the temperature of the reduced pressure polycondensation reaction is 160-240 ℃.
9. The process for producing polyglycolic acid according to claim 1, wherein the polymerization in step 2 is a polycondensation reaction.
10. The method for producing polyglycolic acid according to claim 9, wherein the temperature of the polycondensation reaction is 200 to 220 ℃; the time of the polycondensation reaction is 6-8 h.
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| CN112831031A (en) * | 2021-03-11 | 2021-05-25 | 上海浦景化工技术股份有限公司 | Preparation method of polyglycolic acid |
| CN113045742A (en) * | 2021-03-11 | 2021-06-29 | 上海浦景化工技术股份有限公司 | Preparation method of polyglycolic acid |
| CN114195998A (en) * | 2021-12-27 | 2022-03-18 | 内蒙古久泰新材料有限公司 | Process for preparing high-strength polyglycolic acid by continuous polycondensation |
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| 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 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254411A (en) * | 2013-06-07 | 2013-08-21 | 北京理工大学 | Method for preparing high-molecular-weight polylactic acid through direct polycondensation and chain extension |
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| CN103254411A (en) * | 2013-06-07 | 2013-08-21 | 北京理工大学 | Method for preparing high-molecular-weight polylactic acid through direct polycondensation and chain extension |
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| 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 |
| CN112831031A (en) * | 2021-03-11 | 2021-05-25 | 上海浦景化工技术股份有限公司 | Preparation method of polyglycolic acid |
| CN113045742A (en) * | 2021-03-11 | 2021-06-29 | 上海浦景化工技术股份有限公司 | Preparation method of polyglycolic acid |
| CN115677986A (en) * | 2021-07-27 | 2023-02-03 | 上海浦景化工技术股份有限公司 | Preparation method of thermal aging-resistant degradable aliphatic polyester |
| CN115672214A (en) * | 2021-07-27 | 2023-02-03 | 上海浦景化工技术股份有限公司 | Device and method for preparing polyglycolic acid through low-temperature polymerization |
| CN114276215A (en) * | 2021-11-25 | 2022-04-05 | 上海浦景化工技术股份有限公司 | Method for purifying hexafluoroisopropanol used as GPC test mobile phase and application thereof |
| CN114195998A (en) * | 2021-12-27 | 2022-03-18 | 内蒙古久泰新材料有限公司 | Process for preparing high-strength polyglycolic acid by continuous polycondensation |
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