CN114015030A - Application of L-ascorbic acid and/or L-sodium ascorbate as catalyst for catalyzing ring-opening polymerization reaction of lactone or lactide - Google Patents
Application of L-ascorbic acid and/or L-sodium ascorbate as catalyst for catalyzing ring-opening polymerization reaction of lactone or lactide Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 99
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 51
- 239000002211 L-ascorbic acid Substances 0.000 title claims abstract description 33
- 235000000069 L-ascorbic acid Nutrition 0.000 title claims abstract description 33
- 229960005070 ascorbic acid Drugs 0.000 title claims abstract description 33
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 title claims abstract description 32
- 229960005055 sodium ascorbate Drugs 0.000 title claims abstract description 32
- 150000002596 lactones Chemical class 0.000 title claims abstract description 30
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 15
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 25
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract description 19
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims abstract description 19
- 239000011755 sodium-L-ascorbate Substances 0.000 claims abstract description 19
- 235000019187 sodium-L-ascorbate Nutrition 0.000 claims abstract description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 32
- 239000004626 polylactic acid Substances 0.000 claims description 32
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 28
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 101
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 126
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 78
- 229920001610 polycaprolactone Polymers 0.000 description 52
- 239000000203 mixture Substances 0.000 description 47
- 229920001042 poly(δ-valerolactone) Polymers 0.000 description 47
- 239000004793 Polystyrene Substances 0.000 description 36
- 238000005227 gel permeation chromatography Methods 0.000 description 36
- 229920002223 polystyrene Polymers 0.000 description 36
- 238000001035 drying Methods 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- 238000004821 distillation Methods 0.000 description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000005292 vacuum distillation Methods 0.000 description 9
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 7
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 3
- 229930003268 Vitamin C Natural products 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002954 polymerization reaction product Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 235000019154 vitamin C Nutrition 0.000 description 3
- 239000011718 vitamin C Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 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 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- -1 vitamin C Chemical compound 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- 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
- 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
- C08G63/87—Non-metals or inter-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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an application of L-ascorbic acid and/or L-sodium ascorbate as a catalyst for catalyzing ring-opening polymerization reaction of lactone or lactide; l-ascorbic acid and sodium L-ascorbate are used as catalysts to catalyze the ring-opening polymerization of lactones and lactides (including L-lactide, epsilon-caprolactone, delta-valerolactone and beta-butyrolactone). The yield of the synthesized polymer can reach 99%. In addition, the catalyst provided by the invention can catalyze the ring-opening polymerization reaction of lactone and lactide in air.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to application of L-ascorbic acid and/or L-sodium ascorbate as a catalyst in catalyzing ring-opening polymerization reaction of lactone or lactide.
Background
Polyesters, such as polylactic acid and polycaprolactone, are biodegradable materials and have a wide range of applications in the packaging, biomedical and pharmaceutical industries. The synthesis of the polyester can adopt a method of catalyzing ring-opening polymerization. Stannous octoate is commonly used as a catalyst in industry. In recent years, a large number of metal complex catalysts and organic catalysts have been developed for catalyzing the ring-opening polymerization of polyesters. However, the toxicity of these catalysts is a not negligible problem. The development of non-toxic, inexpensive catalysts remains a goal sought after.
Disclosure of Invention
In view of the above, the present invention provides the use of L-ascorbic acid and/or sodium L-ascorbate as a catalyst for catalyzing the ring-opening polymerization of a lactone or lactide.
The compound is used as a catalyst to catalyze the ring-opening polymerization reaction of lactone or lactide;
the compound is selected from L-ascorbic acid and/or sodium L-ascorbate.
The invention provides a preparation method of polylactic acid, which comprises the following steps:
mixing L-lactide with a catalyst, and carrying out ring-opening polymerization reaction in a solvent to obtain polylactic acid;
the catalyst is L-sodium ascorbate.
In the invention, the molar ratio of the catalyst to the L-lactide is 1: 50-1000;
the temperature of the ring-opening polymerization reaction is 120-170 ℃, and the time is 12-24 h.
The invention provides a preparation method of polylactone, which comprises the following steps:
mixing lactone with a catalyst, and carrying out ring-opening polymerization reaction under the condition of no external solvent to obtain polylactone;
the lactone is epsilon-caprolactone or delta-valerolactone;
the catalyst is L-ascorbic acid or L-sodium ascorbate.
In the invention, the molar ratio of the catalyst to the lactone is 1: 50-400;
the temperature of the ring-opening polymerization reaction is 120-170 ℃, and the time is 12-24 h.
The invention provides a preparation method of polyhydroxybutyrate, which comprises the following steps:
mixing beta-butyrolactone with a catalyst, and carrying out ring-opening polymerization reaction under the condition of no additional solvent to obtain polyhydroxybutyrate;
the catalyst is L-sodium ascorbate.
In the present invention, the molar ratio of the catalyst to β -butyrolactone is 1: 50-400 parts;
the temperature of the ring-opening polymerization reaction is 100-120 ℃, and the time is 12-24 hours.
The invention provides an application of L-ascorbic acid and/or L-sodium ascorbate as a catalyst for catalyzing ring-opening polymerization reaction of lactone or lactide; l-ascorbic acid and sodium L-ascorbate are used as catalysts to catalyze the ring-opening polymerization of lactones and lactides (including L-lactide, epsilon-caprolactone, delta-valerolactone and beta-butyrolactone). The yield of the synthesized polymer can reach 99%. In addition, the catalyst provided by the invention can catalyze the ring-opening polymerization reaction of lactone and lactide in air.
Detailed Description
The invention provides application of a compound as a catalyst for catalyzing ring-opening polymerization reaction of lactone or lactide;
the compound is selected from L-ascorbic acid and/or sodium L-ascorbate.
In the invention, the L-ascorbic acid and/or the L-sodium ascorbate are both natural catalysts; the L-ascorbic acid, namely vitamin C, has a structure shown in a formula (I), and is widely present in fruits and vegetables. Is non-toxic and harmless, and is one of essential vitamins for human body.
Sodium L-ascorbate, the sodium salt of vitamin C, has the structure shown in formula (II) and is the product of vitamin C under alkaline condition.
The invention provides a preparation method of polylactic acid, which comprises the following steps:
mixing L-lactide with a catalyst, and carrying out ring-opening polymerization reaction in a solvent to obtain polylactic acid;
the catalyst is L-sodium ascorbate.
In the invention, the molar ratio of the sodium L-ascorbate to the L-lactide is 1: 50-1000, preferably 1: 100-1000.
The temperature of the ring-opening polymerization reaction of the L-lactide is 120-170 ℃, and the time is 24-96 hours.
In the invention, the solvent adopted by the ring-opening polymerization of the L-lactide is a solvent with a higher boiling point; the solvent is preferably mesitylene, in order to prevent sublimation of the L-lactide.
After the ring-opening polymerization reaction is finished, the obtained ring-opening polymerization reaction product is preferably dissolved by adopting dichloromethane, excessive ethanol is added to precipitate a polymer, and the polymer is filtered and dried to obtain the polylactic acid. The present invention does not specifically limit the amount of dichloromethane used, and the obtained reaction product can be dissolved. The method of filtration and drying is not particularly limited in the present invention, and a technical scheme of filtration and drying well known to those skilled in the art may be adopted. In the invention, the drying is preferably vacuum drying, and the drying time is preferably 24-48 h.
The invention provides a preparation method of polylactone, which comprises the following steps:
mixing lactone with a catalyst, and carrying out ring-opening polymerization reaction under the condition of no external solvent to obtain polylactone;
the lactone is epsilon-caprolactone or delta-valerolactone;
the catalyst is L-ascorbic acid or L-sodium ascorbate.
The invention preferably mixes the lactone and the catalyst under the condition of no water and no oxygen, and carries out ring-opening polymer reaction under the condition of stirring. The source of the epsilon-caprolactone is not particularly limited, and a commercially available epsilon-caprolactone can be used. In the present invention, it is preferable to conduct the ring-opening polymerization after distilling the purchased epsilon-caprolactone commercial product under reduced pressure. The stirring is not particularly limited in the present invention, and a stirring method known to those skilled in the art may be employed.
The two natural catalysts provided by the invention are less in dosage when catalyzing the ring-opening polymerization of epsilon-caprolactone. The ring-opening polymerization reaction needs higher reaction temperature. In the invention, the molar ratio of the catalyst to the lactone is 1: 50-400; preferably 1: 100-400.
The temperature of the lactone ring-opening polymerization reaction is 120-170 ℃, and the time is 24-96 h.
After the ring-opening polymerization reaction is completed, the obtained ring-opening polymerization reaction product is preferably dissolved by dichloromethane, and then excessive ethanol is added to precipitate the polymer, and the polymer is filtered and dried to obtain poly (epsilon-caprolactone) or poly (delta-valerolactone). The invention has no special limit on the dosage of the dichloromethane, and the obtained reaction product can be dissolved; the method for filtering and drying is not particularly limited in the invention, and the technical scheme of filtering and drying which is well known by the technicians in the field can be adopted; in the invention, the drying is preferably vacuum drying, and the drying time is preferably 24-48 h.
The invention provides a preparation method of polyhydroxybutyrate, which comprises the following steps:
mixing beta-butyrolactone with a catalyst, and carrying out ring-opening polymerization reaction under the condition of no additional solvent to obtain polyhydroxybutyrate;
the catalyst is L-sodium ascorbate.
The invention preferably mixes beta-butyrolactone and catalyst under the condition of no water and no oxygen, and carries out ring-opening polymer reaction under the condition of stirring to obtain polyhydroxybutyrate. In the present invention, the source of the beta-butyrolactone is not particularly limited, and a commercially available product of beta-butyrolactone may be used. In the present invention, it is preferable to conduct the ring-opening polymerization after distilling the purchased product of β -butyrolactone under reduced pressure. The stirring is not particularly limited in the present invention, and a stirring method known to those skilled in the art may be employed.
In the invention, the molar ratio of the sodium L-ascorbate to the beta-butyrolactone is 1: 50-400, preferably 1: 100-400; the temperature of the beta-butyrolactone ring-opening polymerization reaction is 120-170 ℃; the time of the beta-butyrolactone ring-opening polymerization reaction is 24-96 hours; preferably 24-48 h.
After the ring-opening polymerization reaction of the beta-butyrolactone is finished, the obtained ring-opening polymerization reaction product is preferably dissolved by dichloromethane, excessive ethanol is added to precipitate the polymer, and the polymer is filtered and dried to obtain polyhydroxybutyrate. The invention has no special limit on the dosage of the dichloromethane, and the obtained reaction product can be dissolved; the method for filtering and drying is not particularly limited in the invention, and the technical scheme of filtering and drying which is well known by the technicians in the field can be adopted; in the invention, the drying is preferably vacuum drying, and the drying time is preferably 24-48 h.
The invention provides two natural compounds, namely L-ascorbic acid and L-sodium ascorbate, which are used as catalysts to catalyze the ring-opening polymerization reaction of lactone and lactide (including L-lactide, epsilon-caprolactone, delta-valerolactone and beta-butyrolactone). The yield of the synthesized polymer can reach 99%. In addition, the catalyst provided by the invention can catalyze the ring-opening polymerization reaction of lactone and lactide in air.
For further illustration of the present invention, the use of L-ascorbic acid and/or sodium L-ascorbate as catalysts for the ring-opening polymerization of lactones or lactides is described in detail below with reference to the examples, which should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
Mixing 10.0mmol of recrystallized L-lactide, 0.1mmol of sodium L-ascorbate and 0.4mL of mesitylene under anhydrous and oxygen-free conditions, stirring the obtained mixture at 170 ℃ for reaction for 24h, adding 10mL of dichloromethane into the obtained mixture to dissolve a polymer, precipitating the polymer by using excessive ethanol, filtering, and drying in vacuum for 24h to obtain the polylactic acid.
The weight of the polylactic acid weighed by the invention is 1.3 g;
the polylactic acid obtained in the embodiment is analyzed by using a gel permeation chromatography with polystyrene as a standard substance, and the number average molecular weight of the obtained polylactic acid is 1.2 ten thousand.
Example 2
Mixing 10.0mmol of recrystallized L-lactide, 0.1mmol of sodium L-ascorbate and 0.4mL of mesitylene under the anhydrous and oxygen-free conditions, stirring the obtained mixture at 120 ℃ for reaction for 24h, adding 10mL of dichloromethane into the obtained mixture to dissolve a polymer, precipitating the polymer by using excessive ethanol, filtering, and drying in vacuum for 24h to obtain the polylactic acid.
The weight of the polylactic acid weighed by the invention is 1.1 g;
the polylactic acid obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polylactic acid was 8.2 kg.
Example 3
Under the anhydrous and oxygen-free conditions, 40.0mmol of recrystallized L-lactide, 0.1mmol of sodium L-ascorbate and 1.6mL of mesitylene are mixed, the obtained mixture is stirred and reacted for 96h at 170 ℃, 40mL of dichloromethane is added into the obtained mixture to dissolve a polymer, excessive ethanol is added into the mixture to precipitate the polymer, and the polymer is filtered and dried for 24h in vacuum to obtain the polylactic acid.
The weight of the polylactic acid weighed by the invention is 5.3 g;
the polylactic acid obtained in the embodiment is analyzed by using a gel permeation chromatography with polystyrene as a standard substance, and the number average molecular weight of the obtained polylactic acid is 1.5 ten thousand.
Example 4
Mixing 100.0mmol of recrystallized L-lactide, 0.1mmol of sodium L-ascorbate and 4.0mL of mesitylene under anhydrous and oxygen-free conditions, stirring the obtained mixture at 170 ℃ for reacting for 96h, adding 100mL of dichloromethane into the obtained mixture to dissolve a polymer, precipitating the polymer by using excessive ethanol, filtering, and drying in vacuum for 24h to obtain the polylactic acid.
The mass of the polylactic acid weighed by the invention is 13.8 g;
the polylactic acid obtained in the embodiment is analyzed by using a gel permeation chromatography with polystyrene as a standard substance, and the number average molecular weight of the obtained polylactic acid is 2.1 ten thousand.
Example 5
Mixing 10.0mmol of recrystallized L-lactide, 0.1mmol of benzyl alcohol, 0.1mmol of sodium L-ascorbate and 4.0mL of mesitylene under anhydrous and oxygen-free conditions, stirring the obtained mixture at 170 ℃ for reaction for 24h, adding 10mL of dichloromethane into the obtained mixture to dissolve a polymer, precipitating the polymer by using excessive ethanol, filtering, and drying in vacuum for 24h to obtain the polylactic acid.
The weight of the polylactic acid weighed by the invention is 1.3 g;
the polylactic acid obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained polylactic acid was 4.9 kg.
Example 6
Mixing 10.0mmol L-lactide, 0.1mmol L-sodium ascorbate and 0.4mL mesitylene in the air, stirring the obtained mixture at 170 ℃ for reaction for 24h, adding 10mL dichloromethane into the obtained mixture to dissolve a polymer, precipitating the polymer by excessive ethanol, filtering, and drying in vacuum for 24h to obtain the polylactic acid.
The weight of the polylactic acid weighed by the invention is 1.3 g;
the polylactic acid obtained in the embodiment is analyzed by using a gel permeation chromatography with polystyrene as a standard substance, and the number average molecular weight of the obtained polylactic acid is 1.1 ten thousand.
Example 7
10.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 170 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of the poly (epsilon-caprolactone) weighed by the invention is 1.0 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the poly (epsilon-caprolactone) obtained was 1.6 ten thousand.
Example 8
10.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 170 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of poly (epsilon-caprolactone) weighed by the invention is 1.1 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the poly (epsilon-caprolactone) obtained was 1.4 ten thousand.
Example 9
10.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 150 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of the poly (epsilon-caprolactone) weighed by the invention is 0.5 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain poly (epsilon-caprolactone) having a number average molecular weight of 5.2 k.
Example 10
10.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 72 hours at 120 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of poly (epsilon-caprolactone) weighed by the invention is 0.1 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain poly (epsilon-caprolactone) having a number average molecular weight of 2.1 thousand.
Example 11
10.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 150 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of the poly (epsilon-caprolactone) weighed by the invention is 0.6 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain poly (epsilon-caprolactone) having a number average molecular weight of 5.8 k.
Example 12
10.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 72 hours at 120 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of poly (epsilon-caprolactone) weighed by the invention is 0.1 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain poly (epsilon-caprolactone) having a number average molecular weight of 2.0 thousand.
Example 13
20.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 48 hours at 170 ℃, 20mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of the poly (epsilon-caprolactone) weighed by the invention is 2.1 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the poly (epsilon-caprolactone) obtained was 2.9 ten thousand.
Example 14
40.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 96 hours at 170 ℃, 40mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of poly (epsilon-caprolactone) weighed by the invention is 4.3 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the poly (epsilon-caprolactone) obtained was 1.5 ten thousand.
Example 15
40.0mmol of epsilon-caprolactone obtained by vacuum distillation and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 96 hours at 170 ℃, 40mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of poly (epsilon-caprolactone) weighed by the invention is 4.4 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the poly (epsilon-caprolactone) obtained was 3.6 ten thousand.
Example 16
10.0mmol of epsilon-caprolactone after reduced pressure distillation, 0.1mmol of benzyl alcohol and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 170 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of the poly (epsilon-caprolactone) weighed by the invention is 1.0 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain poly (epsilon-caprolactone) having a number average molecular weight of 8.8 thousand.
Example 17
10.0mmol of epsilon-caprolactone after reduced pressure distillation, 0.1mmol of benzyl alcohol and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 170 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (epsilon-caprolactone).
The mass of poly (epsilon-caprolactone) weighed by the invention is 1.1 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the poly (epsilon-caprolactone) obtained was 1.1 ten thousand.
Example 18
10.0mmol of. epsilon. -caprolactone and 0.1mmol of L-ascorbic acid were mixed in air, the resulting mixture was stirred at 170 ℃ for 24 hours, 10mL of methylene chloride was added to the resulting mixture to dissolve the polymer, and excess ethanol was added thereto to precipitate the polymer, which was then filtered and vacuum-dried for 24 hours, to obtain poly (. epsilon. -caprolactone).
The mass of the poly (epsilon-caprolactone) weighed by the invention is 0.9 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the poly (epsilon-caprolactone) obtained was 1.1 ten thousand.
Example 19
10.0mmol of epsilon-caprolactone and 0.1mmol of L-sodium ascorbate were mixed in air, the resulting mixture was stirred at 170 ℃ for 24 hours, 10mL of methylene chloride was added to the resulting mixture to dissolve the polymer, and excess ethanol was added thereto to precipitate the polymer, which was filtered and dried in vacuum for 24 hours to obtain poly (. epsilon. -caprolactone).
The mass of the poly (epsilon-caprolactone) weighed by the invention is 1.0 g;
the poly (epsilon-caprolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard, and the number average molecular weight of the poly (epsilon-caprolactone) obtained was 1.3 ten thousand.
Example 20
10.0mmol of delta-valerolactone subjected to reduced pressure distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 170 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the obtained product is filtered and dried for 24 hours in vacuum to obtain poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the invention is 0.7 g;
in the present invention, poly (delta-valerolactone) obtained in the present example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained poly (delta-valerolactone) was 1.2 ten thousand.
Example 21
10.0mmol of delta-valerolactone subjected to reduced pressure distillation and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 170 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the invention is 0.7 g;
in the present invention, poly (delta-valerolactone) obtained in the present example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained poly (delta-valerolactone) was 1.2 ten thousand.
Example 22
10.0mmol of delta-valerolactone subjected to reduced pressure distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 120 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the obtained product is filtered and dried for 24 hours in vacuum to obtain poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the invention is 0.4 g;
the poly (delta-valerolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a poly (delta-valerolactone) having a number average molecular weight of 4.2 k.
Example 23
10.0mmol of delta-valerolactone subjected to reduced pressure distillation and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 120 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the invention is 0.3 g;
the poly (delta-valerolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a poly (delta-valerolactone) having a number average molecular weight of 2.9 kg.
Example 24
20.0mmol of delta-valerolactone subjected to reduced pressure distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 48 hours at 170 ℃, 20mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the obtained product is filtered and dried for 48 hours in vacuum to obtain poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the method is 1.6 g;
in the present invention, poly (delta-valerolactone) obtained in the present example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained poly (delta-valerolactone) was 1.5 ten thousand.
Example 25
20.0mmol of delta-valerolactone subjected to reduced pressure distillation and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 48 hours at 170 ℃, 20mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the obtained product is filtered and dried for 48 hours in vacuum to obtain the poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the method is 1.7 g;
in the present invention, poly (delta-valerolactone) obtained in the present example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained poly (delta-valerolactone) was 1.8 ten thousand.
Example 26
40.0mmol of delta-valerolactone subjected to reduced pressure distillation and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 48 hours at 170 ℃, 40mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the obtained product is filtered and dried for 24 hours in vacuum to obtain poly (delta-valerolactone).
The mass of the poly (delta-valerolactone) weighed by the method is 3.0 g;
in the present invention, poly (delta-valerolactone) obtained in the present example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained poly (delta-valerolactone) was 2.5 ten thousand.
Example 27
40.0mmol of delta-valerolactone subjected to reduced pressure distillation and 0.1mmol of L-sodium ascorbate are mixed under the anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 48 hours at 170 ℃, 40mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the method is 3.1 g;
in the invention, polystyrene is used as a standard substance, and the poly (delta-valerolactone) obtained in the embodiment is analyzed by gel permeation chromatography to obtain the poly (delta-valerolactone) with the number average molecular weight of 2.3 ten thousand.
Example 28
10.0mmol of delta-valerolactone subjected to reduced pressure distillation, 0.1mmol of benzyl alcohol and 0.1mmol of L-ascorbic acid are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred at 170 ℃ for reaction for 24 hours, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried in vacuum for 24 hours to obtain the poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the invention is 0.9 g;
in the invention, polystyrene is used as a standard substance, and the poly (delta-valerolactone) obtained in the embodiment is analyzed by gel permeation chromatography to obtain the poly (delta-valerolactone) with the number average molecular weight of 5.7 thousand.
Example 29
10.0mmol of delta-valerolactone subjected to reduced pressure distillation, 0.1mmol of benzyl alcohol and 0.1mmol of sodium L-ascorbate are mixed under anhydrous and oxygen-free conditions, the obtained mixture is stirred and reacted for 24 hours at 170 ℃, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the polymer is filtered and dried for 24 hours in vacuum to obtain the poly (delta-valerolactone).
The mass of poly (delta-valerolactone) weighed by the invention is 0.9 g;
the poly (delta-valerolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a poly (delta-valerolactone) having a number average molecular weight of 4.7 kg.
Example 30
10.0mmol of delta-valerolactone and 0.1mmol of L-ascorbic acid were mixed in air, the resulting mixture was stirred at 170 ℃ for 24 hours, 10mL of methylene chloride was added to the resulting mixture to dissolve the polymer, and excess ethanol was added thereto to precipitate the polymer, which was filtered and dried in vacuum for 24 hours to obtain poly (. delta. -valerolactone).
The mass of poly (delta-valerolactone) weighed by the invention is 0.9 g;
the poly (delta-valerolactone) obtained in the example was analyzed by gel permeation chromatography using polystyrene as a standard to obtain a poly (delta-valerolactone) having a number average molecular weight of 9.4 k.
Example 31
10.0mmol of delta-valerolactone and 0.1mmol of L-sodium ascorbate were mixed in air, the resulting mixture was stirred at 170 ℃ for 24h, 10mL of dichloromethane was added to the resulting mixture to dissolve the polymer, and excess ethanol was added thereto to precipitate the polymer, which was filtered and dried in vacuum for 24h to obtain poly (. delta. -valerolactone).
The mass of poly (delta-valerolactone) weighed by the invention is 0.9 g;
in the present invention, poly (delta-valerolactone) obtained in the present example was analyzed by gel permeation chromatography using polystyrene as a standard substance, and the number average molecular weight of the obtained poly (delta-valerolactone) was 1.2 ten thousand.
Example 32
Mixing 10.0mmol of beta-butyrolactone subjected to reduced pressure distillation and 0.1mmol of L-sodium ascorbate under anhydrous and oxygen-free conditions, stirring the obtained mixture at 120 ℃ for reaction for 24 hours, adding 10mL of dichloromethane into the obtained reaction solution to dissolve a polymer, precipitating the polymer by using excessive ethanol, filtering, and drying in vacuum for 24 hours to obtain polyhydroxybutyrate.
The mass of polyhydroxybutyrate weighed by the method is 0.8 g;
according to the invention, polystyrene is used as a standard substance, and the polyhydroxybutyrate obtained in the embodiment is analyzed by using gel permeation chromatography, so that the number average molecular weight of the polyhydroxybutyrate is 3.7 thousand.
Example 33
Mixing 10.0mmol of beta-butyrolactone subjected to reduced pressure distillation and 0.1mmol of L-sodium ascorbate under anhydrous and oxygen-free conditions, stirring the obtained mixture at 100 ℃ for reaction for 24 hours, adding 10mL of dichloromethane into the obtained reaction solution to dissolve a polymer, precipitating the polymer by using excessive ethanol, filtering, and drying in vacuum for 24 hours to obtain polyhydroxybutyrate.
The mass of polyhydroxybutyrate weighed by the method is 0.3 g;
according to the invention, polystyrene is used as a standard substance, and the polyhydroxybutyrate obtained in the embodiment is analyzed by using gel permeation chromatography, so that the number average molecular weight of the polyhydroxybutyrate is 1.3 thousand.
Example 34
Under the anhydrous and oxygen-free conditions, 20.0mmol of beta-butyrolactone subjected to reduced pressure distillation and 0.1mmol of L-sodium ascorbate are mixed, the obtained mixture is stirred at 120 ℃ for reaction for 24 hours, 20mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24 hours to obtain polyhydroxybutyrate.
The mass of polyhydroxybutyrate weighed by the method is 1.7 g;
according to the invention, polystyrene is used as a standard substance, and the polyhydroxybutyrate obtained in the embodiment is analyzed by using gel permeation chromatography, so that the number average molecular weight of the polyhydroxybutyrate is 9.7 thousand.
Example 35
Under the anhydrous and oxygen-free conditions, 40.0mmol of beta-butyrolactone subjected to reduced pressure distillation and 0.1mmol of L-sodium ascorbate are mixed, the obtained mixture is stirred at 120 ℃ for reaction for 48 hours, 40mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24 hours to obtain polyhydroxybutyrate.
The mass of polyhydroxybutyrate weighed by the method is 2.8 g;
the polyhydroxybutyrate obtained in the embodiment is analyzed by using polystyrene as a standard substance through gel permeation chromatography, and the number average molecular weight of the polyhydroxybutyrate is 1.7 ten thousand.
Example 36
Under the anhydrous and oxygen-free conditions, 10.0mmol of beta-butyrolactone subjected to reduced pressure distillation, 0.1mmol of benzyl alcohol and 0.1mmol of sodium L-ascorbate are mixed, the obtained mixture is stirred at 120 ℃ for reaction for 24 hours, 10mL of dichloromethane is added into the obtained reaction solution to dissolve a polymer, excessive ethanol is added into the obtained reaction solution to precipitate the polymer, and the obtained product is filtered and dried in vacuum for 24 hours to obtain polyhydroxybutyrate.
The mass of polyhydroxybutyrate weighed by the method is 0.8 g;
according to the invention, polystyrene is used as a standard substance, and the polyhydroxybutyrate obtained in the embodiment is analyzed by using gel permeation chromatography, so that the number average molecular weight of the polyhydroxybutyrate is 3.1 thousand.
As can be seen from the above examples, the present invention provides the use of L-ascorbic acid and/or sodium L-ascorbate as a catalyst for catalyzing the ring-opening polymerization of a lactone or lactide; l-ascorbic acid and/or sodium L-ascorbate are used as catalysts to catalyze the ring-opening polymerization of lactones and lactides (including L-lactide, epsilon-caprolactone, delta-valerolactone and beta-butyrolactone). The yield of the synthesized polymer can reach 99%. In addition, the catalyst provided by the invention can catalyze the ring-opening polymerization reaction of lactone and lactide in air.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The compound is used as a catalyst to catalyze the ring-opening polymerization reaction of lactone or lactide;
the compound is selected from L-ascorbic acid and/or sodium L-ascorbate.
2. A preparation method of polylactic acid comprises the following steps:
mixing L-lactide with a catalyst, and carrying out ring-opening polymerization reaction in a solvent to obtain polylactic acid;
the catalyst is L-sodium ascorbate.
3. The preparation method according to claim 2, wherein the molar ratio of the catalyst to the L-lactide is 1:50 to 1000;
the temperature of the ring-opening polymerization reaction is 120-170 ℃, and the time is 12-24 h.
4. A method for preparing polylactones, comprising the steps of:
mixing lactone with a catalyst, and carrying out ring-opening polymerization reaction under the condition of no external solvent to obtain polylactone;
the lactone is epsilon-caprolactone or delta-valerolactone;
the catalyst is L-ascorbic acid or L-sodium ascorbate.
5. The preparation method according to claim 4, wherein the molar ratio of the catalyst to the lactone is 1:50 to 400;
the temperature of the ring-opening polymerization reaction is 120-170 ℃, and the time is 12-24 h.
6. A preparation method of polyhydroxybutyrate comprises the following steps:
mixing beta-butyrolactone with a catalyst, and carrying out ring-opening polymerization reaction under the condition of no additional solvent to obtain polyhydroxybutyrate;
the catalyst is L-sodium ascorbate.
7. The production method according to claim 6, wherein the molar ratio of the catalyst to β -butyrolactone is 1: 50-400 parts;
the temperature of the ring-opening polymerization reaction is 100-120 ℃, and the time is 12-24 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115612073A (en) * | 2022-11-15 | 2023-01-17 | 中国科学院长春应用化学研究所 | Method for producing polylactic acid and method for producing polylactone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55147510A (en) * | 1979-05-08 | 1980-11-17 | Asahi Chem Ind Co Ltd | Purification of olefin polymer |
| CN103073703A (en) * | 2013-01-29 | 2013-05-01 | 武汉大学 | L-ascorbic acid-6-poly-(epsilon-caprolactone), and synthetic method and controlled release method of L-ascorbic acid-6-poly-(epsilon-caprolactone) |
| CN103382252A (en) * | 2013-07-31 | 2013-11-06 | 暨南大学 | Cyclic biodegradation aliphatic polyester and preparation method thereof |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55147510A (en) * | 1979-05-08 | 1980-11-17 | Asahi Chem Ind Co Ltd | Purification of olefin polymer |
| CN103073703A (en) * | 2013-01-29 | 2013-05-01 | 武汉大学 | L-ascorbic acid-6-poly-(epsilon-caprolactone), and synthetic method and controlled release method of L-ascorbic acid-6-poly-(epsilon-caprolactone) |
| CN103382252A (en) * | 2013-07-31 | 2013-11-06 | 暨南大学 | Cyclic biodegradation aliphatic polyester and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115612073A (en) * | 2022-11-15 | 2023-01-17 | 中国科学院长春应用化学研究所 | Method for producing polylactic acid and method for producing polylactone |
| CN115612073B (en) * | 2022-11-15 | 2024-03-26 | 中国科学院长春应用化学研究所 | Method for producing polylactic acid and method for producing polylactone |
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