CN113527652A - Method for catalyzing lactide ring-opening polymerization by Lewis acid-base pair - Google Patents
Method for catalyzing lactide ring-opening polymerization by Lewis acid-base pair Download PDFInfo
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- CN113527652A CN113527652A CN202110928345.3A CN202110928345A CN113527652A CN 113527652 A CN113527652 A CN 113527652A CN 202110928345 A CN202110928345 A CN 202110928345A CN 113527652 A CN113527652 A CN 113527652A
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- lewis acid
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- polylactide
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 18
- 239000002585 base Substances 0.000 claims abstract description 16
- 239000002841 Lewis acid Substances 0.000 claims abstract description 15
- 239000002879 Lewis base Substances 0.000 claims abstract description 15
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 15
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 2
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 10
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- -1 cyclic ester Chemical class 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 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 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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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
- C08G63/823—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
- C08G63/02—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
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
-
- 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
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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 belongs to the field of chemical industry, and relates to a method for preparing polylactide by using a Lewis acid-base pair. In the invention, the Lewis acid-base pair is successfully used for the ring-opening polymerization reaction of the lactide, can promote the controllable ring-opening polymerization of the lactide, and can prepare the annular polylactide by a simple method. The Lewis acid-base pair synergistically activates the monomers to obtain high molecular weight polylactide. The Lewis acid and base used in the invention have low toxicity and provide a new way for synthesizing environment-friendly polylactide material.
Description
Technical Field
The invention relates to the fields of catalysts and chemical engineering, in particular to a method for catalyzing lactide ring-opening polymerization by a Lewis acid-base pair.
Background
Polylactic acid (PLA) is an important aliphatic polyester material, and has important applications in food packaging, surgical sutures, tissue engineering scaffolds and the like due to its excellent physical properties, biocompatibility and environmental-friendly characteristics.
Polylactic acid is made from fermentation of corn, sugar beet or other biomass into lactic acid. Dimerization of lactic acid produces Lactide (LA) followed by Ring Opening Polymerization (ROP) of the lactide to PLA. The catalyst plays a very critical role in ROP, and stannous octoate (Sn (Oct))2) PLA is produced as a catalyst. Sn (Oct)2Has higher performance in ring-opening polymerizationAnd is capable of producing polymers having a relatively high molecular weight. However, stannous octoate has potential health risks. In addition, PLA is widely used in biomedical applications. Therefore, the development of a non-toxic catalytic system is very important for the application of polylactide in biomedicine. The combination of the most recent lewis acids with nucleophilic organic bases (lewis bases) has been widely used in the polymerization of cyclic esters and polar olefins. Compared with other catalytic systems, the Lewis acid-base pair has more advantages in catalytic polymerization, and the synergistic effect of the Lewis acid and the Lewis base not only improves the catalytic activity, but also widens the selectivity of the cyclic ester.
In view of the above, the present invention provides a novel method for catalyzing the ring-opening polymerization of lactide, that is, the ring-opening polymerization of lactide is catalyzed by using an iron-based lewis acid/organic base binary catalytic system. Iron, as a biocompatible metal, is one of the trace elements essential to the human body. Compared with the prior method, the method provided by the invention has the following advantages: 1) the organic base and the iron Lewis acid used have low toxicity and are easy to remove from the product, and the obtained product can be used in the field of biomedicine and electronic devices; 2) the iron-based Lewis acid used in the system is low in price and is simple and easy to obtain.
Disclosure of Invention
The invention provides a low-toxicity Lewis acid and Lewis base composed of Lewis acid and Lewis base, which has both catalysis and initiation functions, can be used for ring-opening polymerization of lactide, and has extremely high catalytic activity.
The specific technical scheme is as follows:
a Lewis acid-base pair catalyst comprises Lewis acid and Lewis base, wherein the Lewis acid has a general structural formula shown as the following formula (I), and the Lewis base is 1, 8-diazabicycloundecen-7-ene (DBU), 4-Dimethylaminopyridine (DMAP), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD) or 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD).
In the formula:
r is selected from the element Fe;
R1、R2、R3independently selected from alkyl or halogen；
The number of carbon atoms of the alkyl group is 1-16;
preferably, the lewis acid is selected from at least one of ferric chloride (a) and dichloromethyl iron (b). Preferably, the Lewis base is selected from at least one of 1, 8-diazabicycloundecen-7-ene (a), 4-dimethylaminopyridine (b), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (c), 157-triazabicyclo (4.4.0) dec-5-ene (d).
The invention also discloses application of the Lewis acid-base pair catalytic initiator in preparation of polylactide, so as to prove that the Lewis acid-base pair catalytic initiator has excellent catalytic activity.
The application comprises the preparation of polylactide, and in the application, the molar ratio of the Lewis acid to the Lewis base is 0.3/1-3/1; the molar ratio of the Lewis base to the initiator is 0.1/1 to 1/1.
Specifically, when the method is applied to the preparation of polylactide, the lactide is taken as a monomer, the Lewis acid-base pair is taken as a catalyst and an initiator, and homopolymerization is carried out under the condition of bulk.
The initiator can be selectively added in the homopolymerization reaction, on one hand, the effect of adjusting the molecular weight of a polymerization product is achieved, and on the other hand, the Lewis acid-base pair can be accelerated to be dissociated, so that the polymerization reaction speed is accelerated.
Specifically, the initiator is selected from small alcohol molecules, including methanol, ethanol, benzyl alcohol, phenethyl alcohol, terephthalyl alcohol, water and the like.
The temperature of the homopolymerization reaction is 130-180 ℃, and the reaction time is 0.25-24 h.
The invention provides a catalytic initiation system based on a Lewis acid-base pair, which realizes the high-efficiency ring-opening polymerization of lactide monomers and has extremely high reaction activity. Compared with the prior art, the catalytic system has the following remarkable structural characteristics and catalytic effects:
1) when the catalytic system is used for catalyzing the ring-opening polymerization of lactide, the annular polylactide can be obtained through simple synthesis conditions.
2) The catalyst has very low toxicity to human bodies, and can synthesize green, environment-friendly and environment-friendly polylactide.
Drawings
FIG. 1 is a drawing of the polylactide of example 41H NMR spectrum;
FIG. 2 is a GPC chart of polylactides prepared in examples 4, 5 and 6.
Specific examples the present invention is described in further detail below with reference to specific examples, but the embodiments of the present invention are not limited thereto. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Example 1
In N2In a 100mL single-neck flask, benzyl alcohol BnOH (2.1. mu.L, 0.02mmol), ferric chloride (3.2mg,0.02mmol), and DBU (3. mu.L, 0.02mmol) were added under an atmosphere, stirred for 5min, and L-LA (576mg,4mmol) was added. The reaction flask was then placed in an oil bath pan preheated to 130 ℃ and allowed to react for 1 h. The reaction flask was then rapidly cooled to stop the reaction. 4mL of methylene chloride was added to dissolve the sample. Taking a small amount of solution to carry out1H NMR measurement, the remaining solution was settled in 40mL of cold methanol. The resulting polymer was dried overnight in a vacuum oven at 30 ℃.1H NMR measurements showed 95% monomer conversion. The GPC test results show: number average molecular weight Mn24651g/mol, molecular weight distribution of
Example 2
In N2In a 100mL single-neck flask, benzyl alcohol BnOH (2.1. mu.L, 0.02mmol), ferric chloride (3.2mg,0.02mmol), TBD (2.8mg,0.02mmol) were added under an atmosphere, stirred for 5min, and L-LA (288mg,2mmol) was added. The reaction flask was then placed in an oil bath preheated to 130 ℃ and allowed to react for 4.5 h. The reaction flask was then rapidly cooled to stop the reaction. 2mL of methylene chloride was added to dissolve the sample. Taking a small amount of solution to carry out1H NMR measurement, the remaining solution was settled in 20mL of cold methanol. Will be describedThe resulting polymer was dried overnight in a vacuum oven at 30 ℃.1H NMR testing showed 92% monomer conversion. The GPC test results show: number average molecular weight Mn13665g/mol, molecular weight distribution of
Example 3
In N2Benzyl alcohol BnOH (2.1. mu.L, 0.02mmol), ferric chloride (3.2mg,0.02mmol), DMAP (2.4mg,0.02mmol) were added to a 100mL single-neck flask under an atmosphere, stirred for 5min, and L-LA (288mg,2mmol) was added. The reaction flask was then placed in an oil bath preheated to 130 ℃ and allowed to react for 4.5 h. The reaction flask was then rapidly cooled to stop the reaction. 2mL of methylene chloride was added to dissolve the sample. Taking a small amount of solution to carry out1H NMR measurement, the remaining solution was settled in 20mL of cold methanol. The resulting polymer was dried overnight in a vacuum oven at 30 ℃.1H NMR measurements showed a monomer conversion of 94%. The GPC test results show: number average molecular weight Mn13931g/mol, molecular weight distribution of
Example 4
In N2In a 100mL single-neck flask, benzyl alcohol BnOH (2.1. mu.L, 0.02mmol), ferric chloride (3.2mg,0.02mmol), and DBU (3. mu.L, 0.02mmol) were added under an atmosphere, stirred for 5min, and L-LA (576mg,4mmol) was added. Then the reaction flask is put into an oil bath kettle preheated to 180 ℃ for reaction for 2 h. The reaction flask was then rapidly cooled to stop the reaction. 4mL of methylene chloride was added to dissolve the sample. Taking a small amount of solution to carry out1H NMR measurement, the remaining solution was settled in 40mL of cold methanol. The resulting polymer was dried overnight in a vacuum oven at 30 ℃.1H NMR measurements showed a monomer conversion of 94%. The GPC test results show: number average molecular weight Mn27945g/mol, molecular weight distribution of
Example 5
In N2In a 100mL single-neck flask, benzyl alcohol BnOH (2.1. mu.L, 0.02mmol), ferric chloride (3.2mg,0.02mmol), and DBU (3. mu.L, 0.02mmol) were added under an atmosphere, stirred for 5min, and L-LA (864mg,6mmol) was added. Then the reaction flask is put into an oil bath kettle preheated to 180 ℃ for reaction for 2 h. The reaction flask was then rapidly cooled to stop the reaction. 4mL of methylene chloride was added to dissolve the sample. Taking a small amount of solution to carry out1H NMR measurement, the remaining solution was settled in 40mL of cold methanol. The resulting polymer was dried overnight in a vacuum oven at 30 ℃.1H NMR measurements showed 97% monomer conversion. The GPC test results show: number average molecular weight Mn41456g/mol, molecular weight distribution of
Example 6
In N2In a 100mL single-neck flask, benzyl alcohol BnOH (2.1. mu.L, 0.02mmol), ferric chloride (3.2mg,0.02mmol), and DBU (3. mu.L, 0.02mmol) were added under an atmosphere, stirred for 5min, and L-LA (1152mg,8mmol) was added. Then the reaction flask is put into an oil bath kettle preheated to 180 ℃ for reaction for 2 h. The reaction flask was then rapidly cooled to stop the reaction. 8mL of methylene chloride was added to dissolve the sample. Taking a small amount of solution to carry out1H NMR measurement, the remaining solution was settled in 80mL of cold methanol. The resulting polymer was dried overnight in a vacuum oven at 30 ℃.1H NMR measurements showed 98% monomer conversion. The GPC test results show: number average molecular weight Mn55692g/mol, molecular weight distribution of
Example 7
In N2Under the atmosphere, in a 100mL single-necked flask, ferric chloride (3.2mg,0.02mmol) and DBU (3. mu.L, 0.02mmol) were added, and stirred for 5min, followed by addition of L-LA (2304mg,16 mmol). Then the reaction flask is put into an oil bath kettle preheated to 180 ℃ for reaction for 2 h. The reaction flask was then rapidly cooled to stop the reaction. 8mL of methylene chloride was added to dissolve the sample. Taking a small amount of solution to carry out1H NMR measurement, the remaining solution was settled in 80mL of cold methanol. The resulting polymer was dried overnight in a vacuum oven at 30 ℃.1H NMR measurements showed a monomer conversion of 96%. The GPC test results show: number average molecular weight Mn119622g/mol, molecular weight distribution of
The above examples are preferred embodiments of the present invention for the ring-opening polymerization of lactide catalyzed by lewis acid-base pair catalyst system, but the embodiments of the present invention are not limited by the above examples, and any other changes, modifications, substitutions, combinations, simplifications, and equivalents without departing from the spirit and principle of the present invention are all included in the scope of the present invention.
Claims (5)
1. A method for preparing polylactide, comprising the steps of:
uniformly mixing lactide, a Lewis acid-base pair and an initiator, reacting for 0.25-24 h at the temperature of 130-180 ℃, and precipitating in methanol after the reaction is finished to obtain the polylactide.
2. The lewis acid-base pair of claim 1, comprising a lewis acid and a lewis base, wherein the lewis acid is one of ferric chloride and ferric methyl dichloride, and the lewis base is one of 1, 8-diazabicycloundecen-7-ene (DBU), 4-Dimethylaminopyridine (DMAP), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD), and 1,5, 7-triassincyclo (4.4.0) dec-5-ene (TBD).
3. The lewis acid-base pair of claim 2, wherein the molar ratio of lewis acid to lewis base is from 0.3/1 to 3/1; the molar ratio of the Lewis base to the initiator is 0.1/1 to 1/1.
4. The process according to claim 1, wherein the molar ratio of Lewis base to lactide is from 1/50 to 1/1000.
5. The method of claim 1, wherein the initiator is at least one of methanol, ethanol, benzyl alcohol, phenethyl alcohol, terephthalyl alcohol, and water.
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| WO2024087581A1 (en) * | 2022-10-25 | 2024-05-02 | 苏州大学 | Preparation method for cyclic poly(l-lactide) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013227457A (en) * | 2012-04-26 | 2013-11-07 | Hiroshima Univ | Ring-opening polymerization catalyst of cyclic ester and method for ring-opening polymerization of cyclic ester |
| CN106188507A (en) * | 2016-07-08 | 2016-12-07 | 安徽红太阳新材料有限公司 | A kind of synthetic method of high molecular cyclic polylactic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013227457A (en) * | 2012-04-26 | 2013-11-07 | Hiroshima Univ | Ring-opening polymerization catalyst of cyclic ester and method for ring-opening polymerization of cyclic ester |
| CN106188507A (en) * | 2016-07-08 | 2016-12-07 | 安徽红太阳新材料有限公司 | A kind of synthetic method of high molecular cyclic polylactic acid |
Non-Patent Citations (1)
| Title |
|---|
| STEFAN NAUMANN等: ""Cooperative Catalysis for Selective Ring-Opening Polymerization of Lactones: Evolution Towards Simplicity"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 137, no. 45, pages 14439 - 14445 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024087581A1 (en) * | 2022-10-25 | 2024-05-02 | 苏州大学 | Preparation method for cyclic poly(l-lactide) |
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