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 PDFInfo
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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
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- 239000000178 monomer Substances 0.000 title claims abstract description 60
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- -1 cyclic ester Chemical class 0.000 title claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 13
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 150000002924 oxiranes Chemical class 0.000 claims description 6
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical compound C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 claims description 5
- DMSHWWDRAYHEBS-UHFFFAOYSA-N dihydrocoumarin Natural products C1CC(=O)OC2=C1C=C(OC)C(OC)=C2 DMSHWWDRAYHEBS-UHFFFAOYSA-N 0.000 claims description 5
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 5
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 2
- JCVHIWLGFNCDAR-UHFFFAOYSA-N 2-bromo-3-methyloxirane Chemical compound CC1OC1Br JCVHIWLGFNCDAR-UHFFFAOYSA-N 0.000 claims 1
- 238000009396 hybridization Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000012043 crude product Substances 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 229920001519 homopolymer Polymers 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000004062 sedimentation Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000003517 fume Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 4
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 description 3
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 1
- GBYPTTGTFMAEJL-UHFFFAOYSA-N B.Fc1cc(F)c(F)c(F)c1F.Fc1cc(F)c(F)c(F)c1F.Fc1cc(F)c(F)c(F)c1F Chemical compound B.Fc1cc(F)c(F)c(F)c1F.Fc1cc(F)c(F)c(F)c1F.Fc1cc(F)c(F)c(F)c1F GBYPTTGTFMAEJL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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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
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- 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
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- 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
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- 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
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- 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
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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
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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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 |
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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 |
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