CN116813898A - Ring-opening polymerization catalyst for cyclic lactone and preparation method thereof - Google Patents

Ring-opening polymerization catalyst for cyclic lactone and preparation method thereof Download PDF

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CN116813898A
CN116813898A CN202310831763.XA CN202310831763A CN116813898A CN 116813898 A CN116813898 A CN 116813898A CN 202310831763 A CN202310831763 A CN 202310831763A CN 116813898 A CN116813898 A CN 116813898A
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catalyst
opening polymerization
ring
cyclic lactone
solvent
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林雅滢
戴汝熙
徐人威
吴文君
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Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • 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
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a novel catalyst for ring-opening polymerization of cyclic lactone, belonging to the field of high polymer materials. The catalyst is a metal complex having an N, N '-bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine structure, wherein N, N, O, O of the N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine provides one metal binding site, respectively, so that the catalyst can react with an organometallic compound to form the metal complex. The preparation method of the catalyst is simple, the catalyst is low in toxicity and high in efficiency, the ring-opening polymerization of 1, 3-dioxane-2-ketone, L-lactide and epsilon-caprolactone and the copolymerization of L-lactide and epsilon-caprolactone can be catalyzed at a lower temperature, the reaction rate is high, and meanwhile, the catalyst can catalyze the melt polymerization of a body and the polymerization of a solvent-containing system.

Description

Ring-opening polymerization catalyst for cyclic lactone and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a novel cyclic lactone ring-opening polymerization catalyst, and a preparation method and application thereof.
Background
The polyester is a polymer material which is biodegradable, nontoxic, nonirritating and good in biocompatibility. At present, polyester absorbable medical high polymer materials prepared by ring-opening polymerization of a plurality of cyclic lactones are widely used in the medical field as surgical sutures, packages, drug controlled release carriers, tissue engineering stents and the like. Among them, polylactic acid, polycaprolactone, poly 1, 3-dioxane-2-ketone and other medical absorbable polymer materials are paid attention to by more and more laboratories or pharmaceutical enterprises, and the common synthesis method is a ring-opening polymerization method of cyclic lactone, and the synthesis method generally adopts a complex formed by metal and ligand as a catalyst to catalyze the polymerization of monomers. Among them, the most commonly used are organotin-based catalysts such as stannous chloride, stannous octoate, and the like. However, tin-based catalysts require higher reaction temperatures for catalyzing the polymerization of monomers. Meanwhile, the tin element contained in the catalyst belongs to heavy metal elements, and the tin content in the product needs to be strictly controlled so as to avoid toxic and side effects on organisms.
In addition to tin catalysts, ring-opening polymerization catalysts using metals such as aluminum, zinc, iron, titanium, zirconium, and manganese as metal active centers have been reported. As in patent CN 102250137B, a titanium complex is reported as a catalyst for catalyzing lactide polymerization, but the catalyst in the report requires a higher reaction temperature and a longer reaction time for catalyzing the polymerization. Patent CN 108912010B reports that a Schiff base manganese complex is used for catalyzing ring-opening polymerization, but the preparation process of the catalyst is complex and can only be used for solution polymerization. Therefore, the research and preparation process is simple, low in toxicity and high in efficiency, and the novel catalyst not only can be used for bulk melt polymerization, but also can be used for solution polymerization.
Disclosure of Invention
In view of the background, the invention provides a novel cyclic lactone ring-opening polymerization catalyst, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a cyclic lactone ring-opening polymerization catalyst which is a metal complex having an N, N '-bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexanediamine structure, wherein the N, N' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexanediamine has N, N, O, O which each provides a metal binding site so that it can react with an organometallic compound to form a complex, the chemical structural formula of which is specifically:
，
wherein m=ti, zr, r= t Bu、 n Bu。
The preparation method of the cyclic lactone ring-opening polymerization catalyst comprises the following steps:
1) Dissolving N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine in a solvent, adding a metal alkoxide compound under stirring, and reacting for a period of time at a certain temperature;
2) After the reaction is finished, vacuumizing to remove the solvent, and purifying the obtained crude product through recrystallization to obtain the cyclic lactone ring-opening polymerization catalyst.
Further, the molar ratio of N, N' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexanediamine to metal alkoxide used in step 1) is 1:1 to 1:1.2.
Further, the chemical structural formula of the N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine in the step 1) is as follows:
。
further, the metal alkoxide compound in the step 1) is any one of tetrabutyl titanate, zirconium tert-butoxide and titanium tert-butoxide.
Further, the solvent in the step 1) is any one or more of methanol, ethanol, toluene, anhydrous diethyl ether and dichloromethane, and preferably toluene.
Further, the temperature of the reaction in step 1) is 25 ℃ to 80 ℃ and the time is 2 h to 12 h;
further, any one or more of benzene, toluene, xylene, trimethylbenzene, petroleum ether and n-hexane is/are adopted as a solvent for the recrystallization in the step 2), and toluene or n-hexane is preferred.
The cyclic lactone ring-opening polymerization catalyst can be used for preparing absorbable medical high polymer materials, and the application method comprises the following steps:
step one: weighing a monomer and the cyclic lactone ring-opening polymerization catalyst in proportion under the anhydrous and anaerobic condition;
step two: mixing a monomer and the cyclic lactone ring-opening polymerization catalyst under anhydrous and anaerobic conditions, and heating and stirring for a period of time to enable the mixture to undergo ring-opening polymerization reaction;
step three: and cooling the reactant to room temperature, adding a proper amount of good solvent to dissolve the reactant, dripping the obtained solution into the poor solvent after the reactant is completely dissolved, precipitating the polymer, centrifuging to remove the solvent, and drying the precipitate under vacuum to obtain the absorbable medical polymer material.
Further, the molar ratio of the weighed monomer to the cyclic lactone ring-opening polymerization catalyst in the first step is 100:1-7700:1. Further, the molar ratio of the weighed monomer to the titanium-based cyclic lactone ring-opening polymerization catalyst is 1000:1-7700:1, and the molar ratio of the weighed monomer to the zirconium-based cyclic lactone ring-opening polymerization catalyst is 100:1-7700:1.
Further, in the first step, the monomer is any one or two of 1, 3-dioxane-2-ketone, L-lactide and epsilon-caprolactone.
Further, the temperature of the heating and stirring in the second step is 40-140 ℃, preferably 80-110 ℃ and the time is 0.5-h-6 h.
Further, the polymerization reaction in the second step may be carried out under a solvent-free condition or in a solvent, that is, it may be a bulk melt polymerization or a solution polymerization. The reaction solvent is any one or more of tetrahydrofuran, pyridine, toluene, xylene and trimethylbenzene.
Further, in the third step, the good solvent is any one or more of benzene, toluene, benzotrifluoride, xylene, benzyl chloride, trimethylbenzene, tetrahydrofuran, dichloromethane, dichloroethane, chloroform and ethyl acetate.
Further, in the third step, the poor solvent is any one or more of methanol, ethanol, diethyl ether, petroleum ether and n-hexane.
The invention has the beneficial effects that:
(1) The invention provides a novel catalyst for ring-opening polymerization of cyclic lactone, which has low toxicity and high catalytic activity, and can be used for bulk melt polymerization and solution polymerization.
(2) The invention provides a preparation method of a metal complex catalyst with an N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine structure, which has the advantages of simple process, mild reaction conditions and high yield.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the zirconium-based catalyst prepared in example 1.
FIG. 2 is a gel permeation chromatogram of the L-lactide polymer prepared in application example 1.
FIG. 3 is a gel permeation chromatogram of the epsilon caprolactone polymer prepared in application example 4.
FIG. 4 is a gel permeation chromatogram of 1, 3-dioxan-2-one polymer prepared by application example 7.
FIG. 5 is a gel permeation chromatogram of an L-lactide-epsilon-caprolactone copolymer prepared in application example 8.
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of a 1, 3-dioxan-2-one polymer prepared by application example 10.
Detailed Description
A method for preparing a catalyst for ring-opening polymerization of cyclic lactones comprises the following steps:
1) At the temperature of 25-80 ℃, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine and a metal alkoxide compound with the molar ratio of 1:1-1:1.2 are dissolved in a solvent together, and stirred for reaction 2 h-12 h;
2) After the reaction is finished, vacuumizing to remove the solvent, and purifying the obtained crude product through recrystallization to obtain the cyclic lactone ring-opening polymerization catalyst.
Wherein the chemical structural formula of the N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine in the step 1) is as follows:
。
the metal alkoxide compound in the step 1) is any one of tetrabutyl titanate, zirconium tert-butoxide and titanium tert-butoxide.
The solvent in the step 1) is any one or more of methanol, ethanol, toluene, anhydrous diethyl ether and dichloromethane, and toluene is preferred.
And step 2), the recrystallization adopts any one or more of benzene, toluene, xylene, trimethylbenzene, petroleum ether and n-hexane as a solvent.
The chemical structural formula of the ring-opening polymerization catalyst of the cyclic lactone obtained in the step 2) is as follows:
，
wherein m=ti, zr, r= t Bu、 n Bu。
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art.
Example 1
547 mg of N, N' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexanediamine was weighed out in a glove box, 5 mL toluene was added, and the solid was dissolved in toluene with stirring. After the solid was completely dissolved, 384 mg zirconium tert-butoxide was slowly dropped into the solution under stirring, and the resulting mixed solution was reacted at room temperature for 4 hours. After the reaction, toluene was removed by vacuum suction, and the obtained crude product was added to N-hexane to be completely dissolved, concentrated, cooled and crystallized, filtered and dried to obtain a zirconium-based catalyst 664 mg containing an N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine structure, the yield was 84.9%.
Example 2
547 mg of N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine were weighed out in a glove box and dissolved in 5 mL toluene. After the solid was completely dissolved, 341 mg tetrabutyl titanate was slowly dropped into the solution under stirring, and the obtained mixed solution was reacted at room temperature for 4 hours. After the reaction is finished, the toluene is removed by vacuum pumping, the obtained crude product is added into normal hexane to be totally dissolved, concentrated, cooled and crystallized, filtered and dried, and the titanium catalyst 470 mg containing N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine structure is obtained, and the yield is 63.4 percent.
Application example 1
994 mg of L-lactide and 27 mg of the zirconium-based catalyst obtained in example 1 were weighed out in a glove box, and the two were mixed and reacted at 100℃for 4 hours. After the reaction mixture was cooled to room temperature, methylene chloride was added to dissolve it completely. And (3) dripping the obtained dichloromethane solution into absolute ethyl alcohol to obtain white precipitate, centrifuging to remove the solvent, and drying the precipitate in a vacuum drying oven to obtain the L-lactide polymer. The molecular weight of the polymer was found to be 18.7. 18.7 kg/mol and the molecular weight distribution was found to be 1.29 by gel permeation chromatography.
Application example 2
The specific operation of this application example was the same as application example 1, except that the mass of the L-lactide used in the reaction was 1.03. 1.03 g, the mass of the zirconium-based catalyst was 56. 56 mg, and the reaction temperature was increased to 140 ℃. The molecular weight of the obtained polymer was measured by a gel permeation chromatograph and found to be 13.0 kg/mol, and the molecular weight distribution was 1.32.
Application example 3
The specific operation of this application example was the same as that of application example 1, except that the mass of L-lactide used in the reaction was 1.03. 1.03 g, the mass of the zirconium-based catalyst was 56. 56 mg, 1 mL toluene was added to the reaction mixture, and the reaction temperature was increased to 110 ℃. The molecular weight of the obtained polymer was found to be 13.4. 13.4 kg/mol and the molecular weight distribution was found to be 1.47 by gel permeation chromatography.
Application example 4
816 mg ε -caprolactone and 56 mg zirconium-based catalyst obtained in example 1 were weighed in a glove box, mixed and reacted at 80℃for 2 hours. After the reaction mixture was cooled to room temperature, methylene chloride was added to dissolve it completely. And (3) dripping the obtained dichloromethane solution into absolute ethyl alcohol to obtain white precipitate, centrifuging to remove the solvent, and drying the precipitate in a vacuum drying oven to obtain the epsilon-caprolactone polymer. The molecular weight of the polymer was measured by gel permeation chromatography and found to be 51.4. 51.4 kg/mol, and the molecular weight distribution was 1.96.
Application example 5
The specific operation of this application example was the same as that of application example 4, except that the mass of epsilon-caprolactone used in the reaction was 874, 874 mg and the mass of the zirconium-based catalyst was 30 mg. The molecular weight of the obtained polymer was 133.4. 133.4 kg/mol and the molecular weight distribution was 2.13 as measured by gel permeation chromatography.
Application example 6
The specific operation of this application example was the same as that of application example 4, except that epsilon-caprolactone was used in the reaction in a mass of 1.03. 1.03 g and the zirconium-based catalyst in a mass of 10.3. 10.3 mg. The molecular weight of the obtained polymer was 360.2. 360.2 kg/mol and the molecular weight distribution was 2.19 as measured by gel permeation chromatography.
Application example 7
2.2 g of 1, 3-dioxan-2-one and 2.2 mg of the zirconium-based catalyst obtained in example 1 were weighed out in a glove box, mixed and then added to 2.5 mL of toluene to react at 110℃for 2 hours. After the reaction mixture was cooled to room temperature, methylene chloride was added to dissolve it completely. And (3) dripping the obtained dichloromethane solution into absolute ethyl alcohol to obtain white precipitate, centrifuging to remove the solvent, and placing the precipitate into a vacuum drying oven for drying to obtain the 1, 3-dioxane-2-one polymer. The molecular weight of the polymer was found to be 55.2. 55.2 kg/mol and the molecular weight distribution was found to be 2.68 by gel permeation chromatography.
Application example 8
410 mg epsilon-caprolactone, 516 mg L-lactide and 56 mg of the zirconium-based catalyst obtained in example 1 were weighed in a glove box, mixed and reacted at 100℃for 5 hours. After the reaction mixture was cooled to room temperature, methylene chloride was added to dissolve it completely. And (3) dripping the obtained dichloromethane solution into absolute ethyl alcohol to obtain white precipitate, centrifuging to remove the solvent, and drying the precipitate in a vacuum drying oven to obtain the L-lactide-epsilon-caprolactone copolymer. The molecular weight of the polymer was 15.0. 15.0 kg/mol and the molecular weight distribution was 1.31 as measured by gel permeation chromatography.
Application example 9
The specific operation of this application example was the same as that of application example 8, except that 393 mg of epsilon-caprolactone, 496 mg of L-lactide and 27 mg of zirconium-based catalyst were used in the reaction. The molecular weight of the obtained polymer was 19.9. 19.9 kg/mol and the molecular weight distribution was 1.33 as measured by gel permeation chromatography.
Application example 10
2.4 g of 1, 3-dioxan-2-one and 2.4 mg of the titanium-based catalyst obtained in example 2 were weighed out in a glove box, mixed and then added with 2.5 mL toluene to react at 110℃for 2 hours. After the reaction mixture was cooled to room temperature, methylene chloride was added to dissolve it completely. And (3) dripping the obtained dichloromethane solution into absolute ethyl alcohol to obtain white precipitate, centrifuging to remove the solvent, and placing the precipitate into a vacuum drying oven for drying to obtain the 1, 3-dioxane-2-one polymer. The molecular weight of the polymer was 62.4kg/mol and the molecular weight distribution was 1.98 as measured by gel permeation chromatography.
Comparative example
The specific operation of this comparative example was the same as that of application example 6, except that the catalyst used in the reaction was a manganese-based catalyst (its chemical structural formula:) And its mass was 12.0 mg, the mass of epsilon-caprolactone used was 1.20 g. After the reaction mixture was cooled to room temperature, methylene chloride was added to dissolve it completely. The obtained dichloromethane solution was dropped into absolute ethanol, and no precipitate was formed. The titanium-based and zirconium-based catalysts used in the present invention have been demonstrated to have more excellent catalytic performance than the manganese-based catalysts.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. A catalyst for ring-opening polymerization of cyclic lactones, characterized in that the catalyst is a metal complex having the structure of N, N' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexanediamine, and has the chemical structural formula:
，
wherein m=ti, zr, r= t Bu、 n Bu。
2. A process for preparing a catalyst for ring-opening polymerization of a cyclic lactone according to claim 1, comprising the steps of:
1) Dissolving N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine in a solvent, adding a metal alkoxide compound under stirring, and reacting for a period of time at a certain temperature;
2) After the reaction is finished, vacuumizing to remove the solvent, and purifying the obtained crude product through recrystallization to obtain the cyclic lactone ring-opening polymerization catalyst.
3. The process for preparing a catalyst for ring-opening polymerization of cyclic lactone according to claim 2, wherein the molar ratio of N, N' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexanediamine to the metal alkoxide used in step 1) is 1:1 to 1:1.2;
the chemical structural formula of the N, N' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine is as follows:
；
the metal alkoxide compound is any one of tetrabutyl titanate, zirconium tert-butoxide and titanium tert-butoxide.
4. The method for producing a catalyst for ring-opening polymerization of cyclic lactone according to claim 2, wherein the solvent in step 1) is one or more of methanol, ethanol, toluene, dehydrated ether, and methylene chloride.
5. The method for producing a catalyst for ring-opening polymerization of cyclic lactone according to claim 2, wherein the reaction in step 1) is carried out at a temperature of 25 to 80 ℃ for a time of 2 h to 12 h.
6. The method for producing a catalyst for ring-opening polymerization of cyclic lactone according to claim 2, wherein any one or more of benzene, toluene, xylene, trimethylbenzene, petroleum ether and n-hexane is used as a solvent for the recrystallization in step 2).
7. Use of the cyclic lactone ring-opening polymerization catalyst of claim 1 in the preparation of absorbable medical polymer materials, characterized in that the method of application comprises the following steps:
step one: weighing a monomer and the cyclic lactone ring-opening polymerization catalyst in proportion under the anhydrous and anaerobic condition;
step two: mixing a monomer and the cyclic lactone ring-opening polymerization catalyst under anhydrous and anaerobic conditions, and heating and stirring for a period of time to enable the mixture to undergo ring-opening polymerization reaction;
step three: and after the reactant is cooled to room temperature, adding a proper amount of good solvent to dissolve the reactant, then dripping the obtained solution into the poor solvent, precipitating the polymer, centrifuging to remove the solvent, and taking the precipitate and drying the precipitate under vacuum to obtain the absorbable medical polymer material.
8. The use according to claim 7, wherein the molar ratio of the monomer to the cyclic lactone ring-opening polymerization catalyst in step one is from 100:1 to 7700:1; the monomer is any one or two of 1, 3-dioxane-2-ketone, L-lactide and epsilon-caprolactone.
9. The use according to claim 7, wherein the temperature of the heating and stirring in step two is 40 ℃ to 140 ℃ for a period of 0.5 h to 6 h.
10. The use according to claim 7, wherein in step three, the good solvent is any one or more of benzene, toluene, benzotrifluoride, xylene, benzyl chloride, trimethylbenzene, tetrahydrofuran, dichloromethane, dichloroethane, chloroform and ethyl acetate;
the poor solvent is one or more of methanol, ethanol, diethyl ether, petroleum ether and n-hexane.
CN202310831763.XA 2023-07-07 2023-07-07 Ring-opening polymerization catalyst for cyclic lactone and preparation method thereof Pending CN116813898A (en)

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