CN114149571A - Imidazole ionic liquid catalyzed vinyl monomer and cyclic ester monomer hybrid polymerization method - Google Patents

Imidazole ionic liquid catalyzed vinyl monomer and cyclic ester monomer hybrid polymerization method Download PDF

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CN114149571A
CN114149571A CN202111585316.8A CN202111585316A CN114149571A CN 114149571 A CN114149571 A CN 114149571A CN 202111585316 A CN202111585316 A CN 202111585316A CN 114149571 A CN114149571 A CN 114149571A
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cyclic ester
ionic liquid
monomer
monomers
imidazole
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CN114149571B (en
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宋鹏飞
马菊萍
李永莉
马菁菁
袁小龙
席琦
武雪
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Northwest Normal University
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    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloyl morpholine
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a method for catalyzing vinyl monomers and cyclic ester monomers to be hybridized and polymerized by imidazole ionic liquid. The catalytic system used by the hybrid polymerization method is ionic liquid, is green and environment-friendly, has wide monomer application range, is simple and convenient in preparation process, does not need to add additional cocatalyst and initiator, and provides a new idea for synthesizing high-value polymer materials with new characteristics.

Description

Imidazole ionic liquid catalyzed vinyl monomer and cyclic ester monomer hybrid polymerization method
Technical Field
The invention relates to a hybrid polymerization method, in particular to a hybrid polymerization method for catalyzing alkene monomers and cyclic ester monomers by using imidazole ionic liquid.
Background
In conventional copolymerization processes, all monomers must have the same polymeric group (double bond, end group or ring), the polymerization mechanism is essentially the same as for the corresponding homopolymerization, the only difference being the competition between the different monomers. Unlike conventional copolymerization, hybrid copolymerization is the copolymerization of two or more monomers having different polymerizable groups to form the same chain. The cyclic monomer and the vinyl monomer are the most widely used monomers in the polymer industry, and have wide application prospects. Due to the structural differences, the polymerization reactions of cyclic monomers and vinyl monomers generally have very different polymerization mechanisms, catalysts and propagation species. Vinyl monomers are generally polymerized by the radical (or ionic) vinyl addition mechanism, while cyclic monomers are polymerized by the ionic ring opening mechanism. The active breeding species of the vinyl addition mechanism and the ionic ring opening mechanism have strong selectivity on monomers, and are not easy to be mutually converted, so that the establishment of a feasible method for the hybrid copolymerization of vinyl and cyclic monomers and the production of definite copolymers with adjustable components hopefully provide high-value materials with new characteristics.
At present, the reported catalytic systems for hybrid polymerization of vinyl monomers and cyclic ester monomers mainly include the following. In 2012, the group of the tensor subjects (Macromolecules, 2012, 45, 3312-3317) was first found in the phosphazene base (t-BuP)4) Catalytic, small molecule alcohol preparationUnder the condition of an initiator, caprolactone and methyl methacrylate undergo anionic hybrid copolymerization to form a random copolymer, but the catalyst used in the method is poor in universality and expensive. In 2013, the Aoshima group (J. Am. chem. Soc, 2013, 135, 9330-9333) reported tris (pentafluorobenzene) borane (B (C) in Lewis acid6F5)3) The vinyl ether and oxidized isobutylene are subjected to cationic hybrid copolymerization under catalysis, but the preparation condition of the method is harsh, the molecular weight is low, and the distribution is wide. Recently, the Mehrkhodavandi group of topics (ACS Catalysis, 2020, 10(11): 6488-. The Wukubo topic group (Acta Polymer. Sin, 2021, 52, 467-. However, these hybrid polymerization processes in the prior art require multiple steps, involve different catalytic initiation systems, and have metal traces remaining.
Disclosure of Invention
The invention aims to provide a method for catalyzing vinyl monomers and cyclic ester monomers to carry out hybrid polymerization by using imidazole ionic liquid without adding an additional cocatalyst and an initiator.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for catalyzing alkene monomers and cyclic ester monomers to be hybridized and polymerized by imidazole ionic liquid comprises the following specific steps:
respectively taking a catalyst, a vinyl monomer, a cyclic ester monomer and an epoxide according to the mol ratio of 1: 10-100: 10-200; taking an organic solvent according to the proportion that 0.02-0.2 g of catalyst needs 1-5 mL of organic solvent; adding a catalyst, an alkene monomer, a cyclic ester monomer, an epoxide and an organic solvent into a reaction bottle, reacting for 2-12 h at 80-100 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system with chloroform to obtain a crude product; and then, carrying out sedimentation treatment on the crude product by using anhydrous methanol acidified by hydrochloric acid, pouring supernatant, ventilating to volatilize the solvent, and drying at the temperature of 60 ℃ for 10-12 h to obtain the corresponding hybrid copolymer.
The catalyst adopts imidazole ionic liquid, and the anion of the ionic liquid is mainly chloride ion, bromide ion or tetrafluoroborate ion.
The organic solvent adopts tetrahydrofuran or 1, 4-dioxane.
The epoxide is propylene oxide, ethylene oxide, epichlorohydrin, epibromohydrin, styrene oxide or cyclohexene oxide.
The cyclic ester monomer adopts lactide, caprolactone, valerolactone or dihydrocoumarin.
The vinyl monomer adopts methyl methacrylate, methyl acrylate, tert-butyl acrylate, diacetone acrylamide or N-isopropyl acrylamide.
The hybrid polymerization method of the invention utilizes the ionic liquid to realize the hybrid polymerization of the alkene monomer and the cyclic ester monomer. Because the ionic liquid is an environment-friendly solvent, has the advantages of low vapor pressure, good solubility, high stability and adjustable acidity, and has more types and strong designability, the ionic liquid catalyst for hybrid polymerization can be preferably selected, and the high-efficiency hybrid polymerization can be realized. The hybrid polymerization method provided by the invention is suitable for various monomers, and can realize preparation of non-homogeneous monomer copolymers which are difficult to obtain by a conventional polymerization method from methyl methacrylate and cyclic ester monomers which are widely available in industrial sources and low in price. Meanwhile, the hybrid polymerization method adopts a one-step one-pot method to polymerize the alkene monomer and the cyclic ester monomer, and has the advantages of no need of adding additional cocatalyst and initiator, simple and convenient preparation process and post-treatment, and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a copolymer prepared in example 1 of the present invention.
FIG. 2 is a comparison graph of IR spectra of copolymers prepared in example 1 of the present invention and respective homopolymers.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the copolymer prepared in example 2 of the present invention.
FIG. 4 is a nuclear magnetic hydrogen spectrum of the copolymer prepared in example 3 of the present invention.
FIG. 5 is a nuclear magnetic hydrogen spectrum of the copolymer prepared in example 4 of the present invention.
FIG. 6 is a nuclear magnetic hydrogen spectrum of the copolymer prepared in example 5 of the present invention.
FIG. 7 is a nuclear magnetic hydrogen spectrum of the copolymer prepared in example 6 of the present invention.
FIG. 8 is a nuclear magnetic hydrogen spectrum of the copolymer prepared in example 7 of the present invention.
FIG. 9 is a nuclear magnetic hydrogen spectrum of the copolymer prepared in example 8 of the present invention.
FIG. 10 is a diagram showing the combination of reactive monomers according to the present invention.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1
Taking 1-ethyl-3-methylimidazole chloride, lactide, methyl methacrylate and propylene oxide according to the molar ratio of 1:25:25:50, and taking tetrahydrofuran according to the proportion that 0.1g of catalyst needs 5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 2h at 80 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system by using chloroform to obtain a crude product; and (3) carrying out sedimentation treatment on the crude product by using a large amount of anhydrous methanol acidified by hydrochloric acid, pouring a supernatant, volatilizing the solvent in a fume hood, and drying in a vacuum drying oven at the temperature of 60 ℃ for 10 hours to obtain the corresponding hybrid copolymer.
FIG. 1 is a nuclear magnetic hydrogen spectrum of poly (methyl methacrylate-co-lactide) prepared in example 1: (1 H-NMR，CDCl3) Figure (a).
FIG. 2 is a graph comparing the infrared spectra (FTIR) of the poly (methyl methacrylate-co-lactide) prepared in example 1 and the respective homopolymers.
It is evident from the results of fig. 1 and 2 that the polymer obtained in example 1 is a copolymer of methyl methacrylate and lactide, not a mixture of both homopolymers.
Example 2
Taking 1-ethyl-3-methylimidazole chloride, caprolactone, methyl methacrylate and propylene oxide according to the molar ratio of 1:50:50:100, and taking tetrahydrofuran according to the proportion that 0.05g of catalyst needs 2.5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 12h at 100 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system by using chloroform to obtain a crude product; and (3) carrying out sedimentation treatment on the crude product by using a large amount of anhydrous methanol acidified by hydrochloric acid, pouring a supernatant, volatilizing the solvent in a fume hood, and drying in a vacuum drying oven at the temperature of 60 ℃ for 10 hours to obtain the corresponding hybrid copolymer.
FIG. 3 is a nuclear magnetic hydrogen spectrum of poly (methyl methacrylate-co-caprolactone) prepared in example 2: (1 H-NMR，CDCl3) Figure (a).
The polymer prepared in example 2 was a copolymer of methyl methacrylate and caprolactone, rather than a mixture of the two homopolymers.
Example 3
Taking 1-ethyl-3-methylimidazolium bromide, valerolactone, methyl methacrylate and propylene oxide according to the molar ratio of 1:50:50:100, respectively, and taking 1, 4-dioxane according to the proportion that 0.1g of catalyst needs 5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 12h at 80 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system by using chloroform to obtain a crude product; and (3) carrying out sedimentation treatment on the crude product by using a large amount of anhydrous methanol acidified by hydrochloric acid, pouring a supernatant, volatilizing the solvent in a fume hood, and drying in a vacuum drying oven at the temperature of 60 ℃ for 10 hours to obtain the corresponding hybrid copolymer.
FIG. 4 is a nuclear magnetic hydrogen spectrum of poly (methyl methacrylate-co-valerolactone) prepared in example 3: (1 H-NMR，CDCl3) Figure (a).
The polymer prepared in example 3 was a copolymer of methyl methacrylate and valerolactone, rather than a mixture of both homopolymers.
Example 4
Taking 1-ethyl-3-methylimidazole bromide, dihydrocoumarin, methyl methacrylate and propylene oxide according to the molar ratio of 1:25:25:50, and taking 1, 4-dioxane according to the proportion that 0.1g of catalyst needs 5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 12h at 100 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system by using chloroform to obtain a crude product; and (3) carrying out sedimentation treatment on the crude product by using a large amount of anhydrous methanol acidified by hydrochloric acid, pouring a supernatant, volatilizing the solvent in a fume hood, and drying in a vacuum drying oven at the temperature of 60 ℃ for 10 hours to obtain the corresponding hybrid copolymer.
FIG. 5 is a nuclear magnetic hydrogen spectrum of poly (methyl methacrylate-co-dihydrocoumarin) prepared in example 4: (1 H-NMR，CDCl3) Figure (a).
The polymer prepared in example 4 was a copolymer of methyl methacrylate and dihydrocoumarin, rather than a mixture of the two homopolymers.
Example 5
Taking 1-ethyl-3-methylimidazole chloride, lactide, diacetone acrylamide and propylene oxide according to the molar ratio of 1:100:100:200, and taking tetrahydrofuran according to the proportion that 0.2g of catalyst needs 5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 6h at 100 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system by using chloroform to obtain a crude product; and (3) carrying out sedimentation treatment on the crude product by using a large amount of anhydrous methanol acidified by hydrochloric acid, pouring a supernatant, volatilizing the solvent in a fume hood, and drying at the temperature of 60 ℃ in a vacuum drying oven for 12 hours to obtain the corresponding hybrid copolymer.
FIG. 6 is a nuclear magnetic hydrogen spectrum of poly (diacetone acrylamide-co-lactide) prepared in example 5 ((R))1 H-NMR，CDCl3) Figure (a).
The polymer prepared in example 5 was a copolymer of diacetone acrylamide and lactide, rather than a mixture of both homopolymers.
Example 6
Taking 1-ethyl-3-methylimidazole bromide, lactide, N-isopropylacrylamide and propylene oxide according to the molar ratio of 1:100:100:200, and taking 1, 4-dioxane according to the proportion that 0.05g of catalyst needs 2.5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 6h at 100 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system by using chloroform to obtain a crude product; and (3) carrying out sedimentation treatment on the crude product by using a large amount of anhydrous methanol acidified by hydrochloric acid, pouring a supernatant, volatilizing the solvent in a fume hood, and drying at the temperature of 60 ℃ in a vacuum drying oven for 12 hours to obtain the corresponding hybrid copolymer.
FIG. 7 is a nuclear magnetic hydrogen spectrum of poly (N-isopropylacrylamide-co-lactide) prepared in example 6 (M: (M)), (1 H-NMR，CDCl3) Figure (a).
The polymer prepared in example 6 was a copolymer of N-isopropylacrylamide and lactide, instead of a mixture of the two homopolymers.
Example 7
Taking 1-ethyl-3-methylimidazole tetrafluoroborate, lactide, methyl acrylate and propylene oxide according to the molar ratio of 1:25:25:50, and taking tetrahydrofuran according to the proportion that 0.1g of catalyst needs 5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 12h at 100 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system by using chloroform to obtain a crude product; and (3) carrying out sedimentation treatment on the crude product by using a large amount of anhydrous methanol acidified by hydrochloric acid, pouring a supernatant, volatilizing the solvent in a fume hood, and drying at the temperature of 60 ℃ in a vacuum drying oven for 12 hours to obtain the corresponding hybrid copolymer.
FIG. 8 is a nuclear magnetic hydrogen spectrum of poly (methyl acrylate-co-lactide) prepared in example 7: (1 H-NMR，CDCl3) Figure (a).
The polymer prepared in example 7 was a copolymer of methyl acrylate and lactide, rather than a mixture of the two homopolymers.
Example 8
Taking 1-ethyl-3-methylimidazole tetrafluoroborate, lactide, tert-butyl acrylate and propylene oxide according to the molar ratio of 1:50:50:100, and taking tetrahydrofuran according to the proportion that 0.1g of catalyst needs 5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 12h at 100 ℃ in a vacuum atmosphere, cooling to room temperature, and dissolving a reaction system by using chloroform to obtain a crude product; and (3) carrying out sedimentation treatment on the crude product by using a large amount of anhydrous methanol acidified by hydrochloric acid, pouring a supernatant, volatilizing the solvent in a fume hood, and drying at the temperature of 60 ℃ in a vacuum drying oven for 12 hours to obtain the corresponding hybrid copolymer.
FIG. 9 shows the nuclear magnetic hydrogen spectrum of poly (t-butyl acrylate-co-lactide) prepared in example 8: (1 H-NMR，CDCl3) Figure (a).
The polymer prepared in example 8 was a copolymer of t-butyl acrylate and lactide, rather than a mixture of the two homopolymers.
FIG. 10 is a diagram of the reaction process and the structural combination of the reaction monomers involved in the hybrid polymerization method of the present invention. The hybrid polymerization process of methyl methacrylate and lactide in epoxide and tetrahydrofuran is mainly described by taking imidazole ionic liquid as a catalyst, the anions of the imidazole ionic liquid mainly comprise chloride ions, bromide ions and tetrafluoroborate ions, the related cyclic ester monomers also comprise caprolactone, valerolactone and dihydrocoumarin, and the vinyl monomers also comprise methyl acrylate, tert-butyl acrylate, diacetone acrylamide and N-isopropyl acrylamide.

Claims (6)

1. A method for hybrid polymerization of an alkene monomer and a cyclic ester monomer under catalysis of an imidazole ionic liquid is characterized by comprising the following steps: respectively taking a catalyst, a vinyl monomer, a cyclic ester monomer and an epoxide according to the mol ratio of 1: 10-100: 10-200; taking an organic solvent according to the proportion that 0.02-0.2 g of catalyst needs 1-5 mL of organic solvent; adding the raw materials into a reaction bottle, reacting for 2-12 h at 80-100 ℃ in a vacuum atmosphere, cooling to room temperature, dissolving the reaction system with chloroform, and purifying with methanol acidified by hydrochloric acid to obtain the corresponding hybrid copolymer.
2. The method for catalyzing vinyl monomers and cyclic ester monomers to polymerize by hybridization by using the imidazole ionic liquid as claimed in claim 1, wherein the catalyst is the imidazole ionic liquid, and the anion of the ionic liquid is chloride ion, bromide ion or tetrafluoroborate ion.
3. The method for hybrid polymerization of alkene monomers and cyclic ester monomers catalyzed by imidazole-based ionic liquids as claimed in claim 1, wherein the organic solvent is tetrahydrofuran or 1, 4-dioxane.
4. The method for hybrid polymerization of vinyl monomers and cyclic ester monomers catalyzed by imidazole-based ionic liquids as claimed in claim 1, wherein the epoxide is propylene oxide, ethylene oxide, epichlorohydrin, bromopropylene oxide, styrene oxide or cyclohexene oxide.
5. The imidazole-based ionic liquid catalyzed vinyl monomer and cyclic ester monomer hybrid polymerization method according to claim 1, wherein the cyclic ester monomer is lactide, caprolactone, valerolactone or dihydrocoumarin.
6. The imidazole ionic liquid catalyzed vinyl monomer and cyclic ester monomer hybrid polymerization method according to claim 1, wherein the vinyl monomer is methyl methacrylate, methyl acrylate, tert-butyl acrylate, diacetone acrylamide or N-isopropyl acrylamide.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114891200A (en) * 2022-03-29 2022-08-12 浙江皇马科技股份有限公司 Ionic liquid catalyst and method for catalytically synthesizing tetrahydrofuran ethylene oxide copolyether by using same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103044632A (en) * 2012-12-14 2013-04-17 华南理工大学 Hybrid hydrolysis resin, and preparation method and application thereof
US20150018496A1 (en) * 2013-07-10 2015-01-15 National Research Council Of Canada Polyester/Polycarbonate Block Copolymers Via One-Pot, Neat Ring Opening Polymerization
CN110317332A (en) * 2019-07-15 2019-10-11 西北师范大学 It is used to prepare the catalyst system of block polymer and catalyzes and synthesizes the method for block polymer
CN112250882A (en) * 2020-10-28 2021-01-22 上海交通大学 Hybrid polymerization method for methacrylate derivative and cyclic monomer initiated by alkoxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103044632A (en) * 2012-12-14 2013-04-17 华南理工大学 Hybrid hydrolysis resin, and preparation method and application thereof
US20150018496A1 (en) * 2013-07-10 2015-01-15 National Research Council Of Canada Polyester/Polycarbonate Block Copolymers Via One-Pot, Neat Ring Opening Polymerization
CN110317332A (en) * 2019-07-15 2019-10-11 西北师范大学 It is used to prepare the catalyst system of block polymer and catalyzes and synthesizes the method for block polymer
CN112250882A (en) * 2020-10-28 2021-01-22 上海交通大学 Hybrid polymerization method for methacrylate derivative and cyclic monomer initiated by alkoxide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114891200A (en) * 2022-03-29 2022-08-12 浙江皇马科技股份有限公司 Ionic liquid catalyst and method for catalytically synthesizing tetrahydrofuran ethylene oxide copolyether by using same
CN114891200B (en) * 2022-03-29 2023-09-22 浙江皇马科技股份有限公司 Ionic liquid catalyst and method for synthesizing tetrahydrofuran ethylene oxide copolyether by catalysis of ionic liquid catalyst

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