CN113105611B - Polymerization method for ring-opening alternating copolymerization of anhydride compound and epoxy compound - Google Patents
Polymerization method for ring-opening alternating copolymerization of anhydride compound and epoxy compound Download PDFInfo
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- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract
The invention relates to a polymerization method for ring-opening alternating copolymerization of an anhydride compound and an epoxy compound, belonging to the field of polymer synthesis. The invention adopts the combined catalyst to carry out polymerization reaction, and comprises the following steps: under the anhydrous and anaerobic conditions, mixing the combined catalyst, the initiator and the organic solvent, and uniformly stirring; and then adding the first monomer and the second monomer into a polymerization system respectively, and stirring and polymerizing for 0.5-48 hours under the condition of specific temperature to obtain a polyester product. The catalyst composition comprises a first component and a second component, wherein the first component consists of inorganic salt compounds of lithium, sodium, potassium, rubidium and cesium and trialkyl boron compounds. The combined catalyst has the characteristics of low toxicity, commercial availability, low price, high polymerization activity and good chemical selectivity, and has great practical application value.
Description
Technical Field
The invention relates to the field of high polymer synthesis, in particular to a novel, cheap and efficient anhydride/epoxide ring-opening alternating copolymerization method.
Background
With the development of polymer science, the synthetic polymer material has more and more excellent performance, and brings great convenience to human society. The development of a novel high-molecular polymer synthesis method plays an important role in the field of high-molecular materials. Among them, polyester materials have been widely used in the fields of packaging, agriculture, and medicine because of their advantages such as biocompatibility and biodegradability. Therefore, the preparation of polyester materials has become a research hotspot in the field of polymer synthesis. Currently, the preparation of polyester materials mainly comprises the following methods: (1) condensation polymerization of dibasic acid and dihydric alcohol; (2) ring-opening polymerization of cyclic ester monomers; (3) the ring-opening alternating copolymerization of the anhydride and the epoxy compound. Among them, the first method has severe conditions such as vacuum, high temperature and the like required for polymerization, and thus is not widely used; the second method has mild polymerization conditions and controllable polymer molecular weight, is widely favored in recent years, and has been greatly developed, but the structure of the monomer is limited to partial monomers such as lactide and lactone, and the functional modification on the main chain of the polymer is difficult, so that the further application of the method is limited.
Recently, the method of ring-opening alternating copolymerization of anhydride and epoxide has attracted more and more attention due to its advantages of mild polymerization conditions, controllable polymerization, easy functional modification of monomer, etc. The catalysts developed for ring-opening alternating copolymerization at present mainly comprise metal organic catalysts, nonmetal catalysts and the like. The most studied metal organic catalysts mainly comprise complexes of metals such as zinc, cobalt, titanium, chromium and the like, but the complexes have complex structures and complex synthetic methods, and the metal elements generally have high toxicity, so that if the metal elements are remained in the polymer, the application of the polymer in the fields of biomedicine, electronic technology and the like is limited. The non-metal catalyst has been developed in these years, and although the non-metal catalyst solves the problem of metal residue, the price of the non-metal catalyst is still high, and the application value of the non-metal catalyst in industry is limited due to high cost. Therefore, the development of the ring-opening alternating copolymerization catalyst which is green, nontoxic, low in price, good in monomer universality and high in polymerization activity has important significance.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a catalyst combination with environmental protection, no toxicity, low cost, good monomer universality and high polymerization activity, aiming at the current technical situation of preparing polyester by ring-opening alternating copolymerization, and the polyester prepared by the catalyst combination has the advantages of regular structure, controllable molecular weight and narrow molecular weight distribution (as shown in fig. 1).
The second technical problem to be solved by the invention is to provide a ring-opening alternating copolymerization method based on the catalyst combination.
In order to solve the technical problems, the invention adopts the technical scheme that:
the polymerization reaction is carried out by adopting the combined catalyst, and the method comprises the following steps:
a. under the anhydrous and anaerobic conditions, mixing the combined catalyst, the initiator and the organic solvent, and uniformly stirring to form a polymerization system, wherein the concentration of the catalyst is 3-30 mmol/L;
b. adding the first monomer and the second monomer into the polymerization system respectively, and stirring and polymerizing for 0.5-48 hours at the temperature of 25-150 ℃;
c. after the polymerization is finished, stopping the reaction by using hydrochloric acid/ethanol solution, settling by using a large amount of ethanol, and filtering to separate out precipitate;
d. and (3) pumping the precipitate to constant weight in a vacuum oven at 50 ℃ to obtain a polyester product.
In the above technical solution, the combined catalyst comprises a first component and a second component, the first component is preferably one or more selected from hydroxides, carbonates, phosphates, monohydrogen phosphates of lithium, sodium, potassium, rubidium and cesium, and hydrates thereof, and the second component is an organoboron compound (as shown in fig. 2). The first component can also catalyze the ring-opening alternating copolymerization independently, but the effect of adding the second component is to inhibit side reactions such as ester exchange.
In the technical scheme, the molar ratio of the first component to the second component is 1:0-1: 10.
In the above technical scheme, the initiator may be at least one of water, any alcohol, and any organic acid.
In the above technical solution, the first monomer may be at least one of any cyclic anhydride compound, and the second monomer may be at least one of any alkylene oxide and glycidyl ether. Preferably, the first monomer is one or more of phthalic anhydride, camphoric anhydride, nadic anhydride, methylnadic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, adipic anhydride and diglycolic anhydride; the second monomer is preferably one or more of cyclohexene oxide, ethylene oxide, propylene oxide, epichlorohydrin, 1-butylene oxide, 1-hexylene oxide, 1, 2-dimethylethylene oxide, 3, 4-epoxytetrahydrofuran, styrene oxide, n-butyl glycidyl ether, allyl glycidyl ether, tert-butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether.
In the above technical solution, the molar ratio of the first monomer and the second monomer is preferably 1:1 to 1: 10.
In the above technical solution, the organic solvent is selected from aprotic organic solvents or their mixture in any proportion, such as benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyltetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide or their mixture in any proportion.
In the technical scheme, the molar ratio of the catalyst to the initiator is 1:1-1: 50.
In the present invention, the molecular weight, structure, etc. of the polymer are tested by the following methods:
(1) molecular weight: the polymer samples were analyzed for number average molecular weight (Mn) and Molecular Weight Distribution (MWD) using a gel permeation chromatograph model TOSOH HLC-8220SEC with tetrahydrofuran as eluent and polystyrene as standard at a rate of 1ml/min at a temperature of 40 ℃, where the chromatographic column was Super HZM-Hx3.
(2) Polymer structure: the structure of the polymer sample was characterized using Nuclear Magnetic Resonance (NMR) under the test conditions: using CDCl at a temperature of 25 deg.C3The solvent was used to prepare a solution with a concentration of 0.1g/mL for testing.
Has the advantages that:
at present, the catalyst for preparing polyester by ring-opening alternating copolymerization is generally a metal organic complex with a complex structure and a complicated synthesis method, or an expensive organic base catalyst, and has great limitation in practical application. The invention adopts the most conventional alkali metal inorganic compound as the catalyst, has the characteristics of low toxicity, commercial availability, low price, high polymerization activity and good chemical selectivity, and has great practical application value.
Drawings
FIG. 1 is a reaction equation of ring-opening alternating copolymerization of an acid anhydride compound and an epoxy compound;
FIG. 2 is a schematic structural view of a second component;
FIG. 3 is a gel permeation chromatogram of a polymer prepared in example 1 of the present invention;
FIG. 4 is a NMR spectrum of a polymer prepared in example 1 of the present invention;
FIG. 5 is a gel permeation chromatogram of a polymer prepared in example 3 of the present invention;
FIG. 6 shows the NMR spectrum of the polymer prepared in example 3 of the present invention.
Wherein:
r1, R2 and R3 of FIG. 2 are, identically or differently, selected from hydrogen, halogen, C1-C20 alkyl or C4-C20 aryl;
in FIG. 4, peaks No. 1 at 5.7 to 6.0ppm and peaks No. 2 at 4.4 to 4.7ppm are the resonance peaks of the polyester unit (integrated areas are A, respectively)1And A2) The peak having a chemical shift of 3.5ppm is the formant of the polyether unit (integrated area A)3). The content of polyester units in the obtained polymer was: [ (A)1+A2)/3]/[(A1+A2)/3+A3/3]＝98.4％；
In FIG. 6, peaks No. 1 at 5.4 to 5.5ppm and peaks No. 2 at 4.2 to 4.5ppm are the resonance peaks of the polyester unit (integrated areas are A, respectively)1And A2) The peak having a chemical shift of 3.4 to 3.6ppm is the formant of the polyether unit (integrated area A)3). The content of polyester units in the obtained polymer was: [ (A)1+A2)/3]/[(A1+A2)/3+A3/3]＝98.0％。
Detailed Description
The present invention will be described in further detail with reference to examples.
The following examples are briefly described as follows:
under the anhydrous and anaerobic conditions, mixing the catalyst, the initiator and the organic solvent, and uniformly stirring; then adding the first monomer and the second monomer into a polymerization system respectively, and stirring and polymerizing for 0.548 hour under the condition of specific temperature; after the polymerization is finished, the reaction is stopped by hydrochloric acid/ethanol solution, after a large amount of ethanol is used for settling, precipitate is filtered and separated out, and then the precipitate is dried in a vacuum oven at the temperature of 50 ℃ until the weight is constant, so that a polyester product is obtained.
Example 1
Under the anhydrous and oxygen-free conditions, potassium carbonate (2.8mg, 0.02mmol) and benzyl alcohol (10.8mg, 0.1mmol) are weighed, added into 1ml of tetrahydrofuran and stirred uniformly; phthalic anhydride (0.74g, 5mmol) and propylene oxide (1.45g, 25mmol) were added to the above solution, and the reaction was stirred at 100 ℃ for 24 hours; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (phthalic anhydride-alt-propylene oxide).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the phthalic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn5.3kg/mol, molecular weight distribution 1.15 (as shown in FIG. 3); phthalic anhydride and propylene oxide are arranged alternately on the polymer chain, and the proportion of polyester units can reach 98.4% (as shown in FIG. 4).
Example 2
Weighing sodium carbonate (2.1mg, 0.02mmol) and benzyl alcohol (10.8mg, 0.1mmol) under anhydrous and oxygen-free conditions, measuring triethylboron (60ul, 0.06mmol), mixing with camphoric anhydride (0.91g, 5mmol) and allyl glycidyl ether (2.85g, 25mmol), and stirring at 60 deg.C for 48 hr; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (camphoric anhydride-alt-allyl glycidyl ether).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the phthalic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn7.3kg/mol, molecular weight distribution 1.17; the camphoric anhydride and the allyl glycidyl ether are alternately arranged on a polymer chain, and the proportion of the polyester unit can reach 98.1 percent.
Example 3
Lithium carbonate (1.5mg, 0.02mmol) and benzyl alcohol (10.8mg, 0.1mmol) were weighed out under anhydrous and oxygen-free conditions, triethylboron (100ul, 0.1mmol) was weighed out, and thoroughly mixed with phthalic anhydride (0.74g, 5mmol) and allyl glycidyl ether (2.45g, 25mmol), followed by stirring reaction at 80 ℃ for 48 hours; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (phthalic anhydride-alt-allyl glycidyl ether).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the phthalic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn5.4kg/mol, a molecular weight distribution of 1.18 (as shown in FIG. 5), phthalic anhydride and allyl glycidyl ether arranged alternately on the polymer chain, and the proportion of polyester units reached 98.0% (as shown in FIG. 6).
Example 4
Weighing potassium phosphate (4.2mg, 0.02mmol) and benzyl alcohol (10.8mg, 0.1mmol) under anhydrous and oxygen-free conditions, measuring triethylboron (60ul, 0.06mmol), mixing with phthalic anhydride (0.74g, 5mmol) and epoxycyclohexane (2.45g, 25mmol), and stirring at 100 deg.C for reaction for 4 hr; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (phthalic anhydride-alt-epoxycyclohexane).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the phthalic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn7.6kg/mol, molecular weight distribution 1.15, phthalic anhydrideThe formic anhydride and the cyclohexene oxide are alternately arranged on a polymer chain, and the proportion of the polyester unit can reach 98.4 percent.
Example 5
Weighing potassium carbonate (2.8mg, 0.02mmol) and benzyl alcohol (5.4mg, 0.05mmol) under anhydrous and anaerobic conditions, mixing with phthalic anhydride (0.74g, 5mmol) and cyclohexene oxide (1.47g, 15mmol), and stirring at 60 deg.C for 24 hr; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (phthalic anhydride-alt-epoxycyclohexane).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the phthalic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn14.5kg/mol, molecular weight distribution 1.16; phthalic anhydride and cyclohexene oxide are arranged alternately on the polymer chain, and the proportion of polyester units can reach 98.9%.
Example 6
Under the anhydrous and anaerobic conditions, potassium carbonate (2.8mg, 0.02mmol) and benzoic acid (6.1mg, 0.05mmol) are weighed and added into 2ml of toluene, and the mixture is stirred uniformly; phthalic anhydride (1.48g, 10mmol) and cyclohexene oxide (1.45g, 25mmol) were added to the above solution, and the mixture was stirred at 60 ℃ for reaction for 24 hours; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (phthalic anhydride-alt-epoxycyclohexane).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the phthalic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn24.8kg/mol, molecular weight distribution 1.12; phthalic anhydride and cyclohexene oxide are arranged alternately on the polymer chain, and the proportion of polyester units can reach 97.6%.
Example 7
Under the anhydrous and anaerobic conditions, potassium dihydrogen phosphate (3.5mg, 0.02mmol) and benzyl alcohol (5.4mg, 0.05mmol) are weighed and added into 3ml of 1, 4-dioxane to be uniformly stirred; phthalic anhydride (1.48g, 10mmol) and styrene oxide (3g, 25mmol) were added to the above solution, and the reaction was stirred at 80 ℃ for 24 hours; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (phthalic anhydride-alt-styrene oxide).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the phthalic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn25.4kg/mol, molecular weight distribution 1.14; phthalic anhydride and styrene oxide are arranged alternately on the polymer chain, and the proportion of polyester units can reach 98.0%.
Example 8
Weighing potassium carbonate (2.8mg, 0.02mmol) and distilled water (1.8mg, 0.1mmol) under anhydrous and anaerobic conditions, measuring triethylboron (60ul, 0.06mmol), mixing with phthalic anhydride (0.74g, 5mmol) and n-butyl glycidyl ether (3.25g, 25mmol), and stirring at 100 deg.C for 4 hr; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (phthalic anhydride-alt-n-butyl glycidyl ether).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the phthalic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn9.5kg/mol, a molecular weight distribution of 1.16, phthalic anhydride and n-butyl glycidyl ether arranged alternately on the polymer chain, and the proportion of polyester units up to 98.5%.
Example 9
Weighing potassium carbonate (2.8mg, 0.02mmol) and distilled water (1.8mg, 0.1mmol) under anhydrous and anaerobic conditions, measuring triethylboron (60ul, 0.06mmol), mixing with maleic anhydride (0.98g, 10mmol) and cyclohexene oxide (4.90g, 50mmol), and stirring at 60 deg.C for 48 hr; after the polymerization is finished, adding 1ml of 10% hydrochloric acid/ethanol (v/v) solution into a polymerization system to terminate the reaction; the polymer was precipitated with 100ml of ethanol and dried in a vacuum oven at 50 ℃ to constant weight to give poly (maleic anhydride-alt-epoxycyclohexane).
The monomer conversion rate, the number average molecular weight, the molecular weight distribution and the chemical composition are characterized by adopting a gel permeation chromatography and nuclear magnetic resonance hydrogen spectrum method, the conversion rate of the maleic anhydride monomer is 100 percent, and the number average molecular weight M of the obtained polymer isn9.5kg/mol, a molecular weight distribution of 1.16, maleic anhydride and epoxycyclohexane arranged alternately in the polymer chain, the proportion of polyester units amounting to 98.2%.
Claims (6)
1. A polymerization method for ring-opening alternating copolymerization of an anhydride compound and an epoxy compound is characterized in that a combined catalyst is adopted for polymerization reaction, and the method comprises the following steps:
a. under the anhydrous and anaerobic conditions, mixing the combined catalyst, the initiator and the organic solvent, and uniformly stirring to form a polymerization system, wherein the concentration of the catalyst is 3-30 mmol/L; the combination catalyst comprises a first component and a second component, wherein the first component is one or more of carbonates, phosphates, monohydrogen phosphates and hydrates of lithium, sodium, potassium, rubidium and cesium, and the second component is an organic boron compound;
b. adding the first monomer and the second monomer into the polymerization system respectively, and stirring and polymerizing for 0.5-48 hours at the temperature of 25-150 ℃; the first monomer is at least one of any cyclic anhydride compounds; the second monomer is at least one of any oxyalkylene and glycidyl ether;
c. after the polymerization is finished, stopping the reaction by using hydrochloric acid/ethanol solution, settling by using a large amount of ethanol, and filtering to separate out precipitate;
d. and (3) pumping the precipitate to constant weight in a vacuum oven at 50 ℃ to obtain a polyester product.
2. The polymerization process for ring-opening alternating copolymerization of an acid anhydride compound and an epoxy compound according to claim 1, wherein the molar ratio of the second component to the first component is greater than 0:1 and equal to or less than 10: 1.
3. The method for ring-opening alternating copolymerization of an acid anhydride compound and an epoxy compound according to claim 1, wherein the initiator is at least one of water, any alcohol, and any organic acid.
4. The method for polymerizing the ring-opening alternating copolymerization of the acid anhydride compound and the epoxy compound according to claim 1, wherein the molar ratio of the first monomer to the second monomer is 1:1 to 1: 10.
5. The method for polymerizing the acid anhydride compound and the epoxy compound by ring-opening alternating copolymerization of claim 1, wherein the organic solvent is an aprotic organic solvent or a mixture thereof in any ratio.
6. The method for ring-opening alternating copolymerization of an acid anhydride compound and an epoxy compound according to any one of claims 1 to 5, wherein the molar ratio of the catalyst to the initiator is 1:1 to 1: 50.
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| CN113912829B (en) * | 2021-11-14 | 2023-04-21 | 福州大学 | Method for catalyzing ring-opening copolymerization of epoxide and cyclic anhydride by metal organic framework |
| CN114349791B (en) * | 2022-01-14 | 2024-02-09 | 南京大学 | Mononuclear chromium complex, preparation method and catalytic application thereof |
| CN115286778B (en) * | 2022-08-31 | 2023-04-07 | 天津大学 | Method for preparing polyester dihydric alcohol by reversible-inactivation ring-opening alternating copolymerization |
| CN115536825A (en) * | 2022-11-15 | 2022-12-30 | 中国科学院长春应用化学研究所 | Copolymerization method of anhydride and epoxy catalyzed by fluorine catalyst |
| CN116284830A (en) * | 2023-04-06 | 2023-06-23 | 福州大学 | Zirconium-based metal organic framework material and application thereof in catalytic ring-opening copolymerization |
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