CN114478635B - Chromium compound, preparation method thereof and preparation method of multi-block polyester material - Google Patents
Chromium compound, preparation method thereof and preparation method of multi-block polyester material Download PDFInfo
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- CN114478635B CN114478635B CN202210124500.0A CN202210124500A CN114478635B CN 114478635 B CN114478635 B CN 114478635B CN 202210124500 A CN202210124500 A CN 202210124500A CN 114478635 B CN114478635 B CN 114478635B
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- 150000001845 chromium compounds Chemical class 0.000 title claims abstract description 72
- 229920000728 polyester Polymers 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 17
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 150000002118 epoxides Chemical class 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 37
- -1 cyclic ester Chemical class 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical group C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 claims description 4
- 125000006239 protecting group Chemical group 0.000 claims description 4
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical group [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 claims description 3
- XYWBVUWVYIRQHN-UHFFFAOYSA-N [N+](=O)([O-])[Cr][N+](=O)[O-] Chemical compound [N+](=O)([O-])[Cr][N+](=O)[O-] XYWBVUWVYIRQHN-UHFFFAOYSA-N 0.000 claims description 3
- LRCIYVMVWAMTKX-UHFFFAOYSA-L chromium(ii) acetate Chemical compound [Cr+2].CC([O-])=O.CC([O-])=O LRCIYVMVWAMTKX-UHFFFAOYSA-L 0.000 claims description 3
- XZQOHYZUWTWZBL-UHFFFAOYSA-L chromium(ii) bromide Chemical compound [Cr+2].[Br-].[Br-] XZQOHYZUWTWZBL-UHFFFAOYSA-L 0.000 claims description 3
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 abstract description 28
- 229920000515 polycarbonate Polymers 0.000 abstract description 20
- 239000004417 polycarbonate Substances 0.000 abstract description 20
- 229920000642 polymer Polymers 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 239000002262 Schiff base Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 150000004753 Schiff bases Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 55
- 238000006243 chemical reaction Methods 0.000 description 53
- 239000007795 chemical reaction product Substances 0.000 description 32
- 238000004458 analytical method Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 238000004062 sedimentation Methods 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910052805 deuterium Inorganic materials 0.000 description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 3
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- LWFZZYSDYXSRSX-UHFFFAOYSA-N [O].[N+](=O)([O-])C1=C(C=CC(=C1)[N+](=O)[O-])O Chemical compound [O].[N+](=O)([O-])C1=C(C=CC(=C1)[N+](=O)[O-])O LWFZZYSDYXSRSX-UHFFFAOYSA-N 0.000 description 2
- SGXJIMGHOCRJJW-UHFFFAOYSA-N [O].[N+](=O)([O-])C1=C(C=CC=C1)O Chemical compound [O].[N+](=O)([O-])C1=C(C=CC=C1)O SGXJIMGHOCRJJW-UHFFFAOYSA-N 0.000 description 2
- DUZNLCNPJVJPHK-UHFFFAOYSA-N [O].[N+](=O)([O-])C1=CC=C(C=C1)O Chemical compound [O].[N+](=O)([O-])C1=CC=C(C=C1)O DUZNLCNPJVJPHK-UHFFFAOYSA-N 0.000 description 2
- LCZSFVMKKSGELK-UHFFFAOYSA-N [O].[N+](=O)([O-])C=1C=C(C=C(C=1)[N+](=O)[O-])O Chemical compound [O].[N+](=O)([O-])C=1C=C(C=C(C=1)[N+](=O)[O-])O LCZSFVMKKSGELK-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-M p-toluate Chemical compound CC1=CC=C(C([O-])=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-M 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- DSXKMMAQDSAZAC-UHFFFAOYSA-N 2-hydroxy-3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C)=C(O)C(C=O)=C1 DSXKMMAQDSAZAC-UHFFFAOYSA-N 0.000 description 1
- ROILLNJICXGZQQ-UHFFFAOYSA-N 3-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC=CC(C=O)=C1O ROILLNJICXGZQQ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010197 meta-analysis Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AKVIZYGPJIWKOS-UHFFFAOYSA-N tert-butyl n-(2-aminocyclohexyl)carbamate Chemical compound CC(C)(C)OC(=O)NC1CCCCC1N AKVIZYGPJIWKOS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
-
- 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
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
Abstract
The invention provides a chromium compound, which has a structure shown in a formula (I); the chromium compound provided by the invention is formed by chelating metal chromium with a ligand containing a Schiff base bond and a catalyst structure, and has catalytic performance which shows special catalytic performance compared with complexes such as Schiff base chromium and the like: catalytic epoxide and CO 2 The copolymerization reaction can maintain excellent catalytic activity and high polycarbonate segment selectivity in a wider range; can catalyze epoxide and CO by a one-pot one-step method 2 And cyclic esters to give multiblock polymers. Experimental results show that the chromium compound is used for catalyzing the epoxy cyclohexane and CO 2 And epsilon-caprolactone ternary polymerization reaction to obtain the multi-block polyester material with molecular weight of 45kDa.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to a chromium compound, a preparation method thereof and a preparation method of a multi-block polyester material.
Background
The degradable high polymer material is a substitute product of the traditional non-degradable high polymer material, can relieve white pollution, and has synthesis and performance characterization as a research hot spot at present.
Polyester materials represented by polylactic acid and polycaprolactone have been widely used in the fields of disposable tableware, packaging materials and biological tissue engineering, however, the single structure of these polyester materials results in a smaller adjustment range of material properties. Epoxide with CO 2 Is prepared through copolymerization reaction to obtain degradable polymerThe polycarbonate material has the advantages of abundant monomer substitution structure, wide sources and CO with' greenhouse gas 2 Is C1 source and the like, and is also paid attention to by scientific researchers.
epoxide/CO 2 The copolymer chain segment and the polyester chain segment are linked into a copolymer, so that the performance among the chain segments can be combined to improve the material performance; the copolymerization of the three-component monomers under the action of a one-component catalyst generally results in a two-block copolymer, which is affected by the reactivity difference between the different monomers. However, there may be a lack of incompatibility between the segments of the two-block copolymers, for which purpose the preparation of multi-block polyester materials of shorter chain length can simultaneously achieve the purposes of combining material properties and improving material compatibility. Therefore, it is of great importance to provide a multi-block polyester material as described above.
Disclosure of Invention
The technical problem solved by the invention is to provide a chromium compound which can still maintain excellent catalytic performance at higher temperature and catalyze epoxide and CO at 100 DEG C 2 The selectivity of the polycarbonate unit in the copolymerization reaction is maintained above 99%.
The application also provides a chromium compound which has a structure shown in a formula (I):
wherein R is 1 ～R 8 Each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, hydroxy, nitro, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C3-C40 siloxy, substituted or unsubstituted C1-C20 acyl, substituted or unsubstituted C2-C20 alkoxycarbonyl, substituted or unsubstituted C2-C20 acyloxy, substituted or unsubstituted C2-C20 amido, substituted or unsubstituted C2-C20 alkoxycarbonylaminoThe C7-C20 aryloxycarbonylamino group, the substituted or unsubstituted C1-C20 sulfamoyl amino group, the substituted or unsubstituted C1-C20 sulfonyl group, the substituted or unsubstituted C1-C20 alkylthio group, the substituted or unsubstituted C6-C20 arylthio group, the substituted or unsubstituted C1-C20 heterocyclic thio group, the substituted or unsubstituted C1-C20 ureido group, the substituted or unsubstituted C3-C40 silyl group or any two substituents form a condensed ring with the benzene ring;
x is independently selected from anionic groups.
Preferably, said R 1 ～R 8 Each independently selected from hydrogen, halogen, cyano, hydroxy, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxy; the X is selected from F, cl, br, I, NO 3 、CH 3 COO、CCl 3 COO、CF 3 COO、ClO 4 P-methylbenzoate, p-toluenesulfonate, 2, 4-dinitrophenol oxygen, 3, 5-dinitrophenol oxygen, p-nitrophenol oxygen or o-nitrophenol oxygen.
Preferably, said R 2 、R 4 、R 6 And R is 8 Are all selected from hydrogen, R is 1 、R 3 、R 5 And R is 7 Each independently selected from t-butyl, methyl or hydrogen.
The application also provides a preparation method of the chromium compound, which comprises the following steps:
a) Reacting a compound having the structure of formula (VI) with a compound having the structure of formula (VII) to obtain a compound having the structure of formula (V);
b) Removing Boc protecting groups from the compound with the structure of formula (V) under the action of trifluoroacetic acid to obtain a compound with the structure of formula (III);
c) Reacting a compound with a structure of formula (III) with a substituted salicylaldehyde with a structure of formula (IV) to obtain a ligand with a structure of formula (II);
d) Reacting a ligand with a structure shown in a formula (II) with a chromium compound in a solvent to obtain a chromium compound with a structure shown in a formula (I);
wherein R is 1 ～R 8 Each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, hydroxy, nitro, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C3-C40 siloxy, substituted or unsubstituted C1-C20 acyl, substituted or unsubstituted C2-C20 alkoxycarbonyl, substituted or unsubstituted C2-C20 acyloxy, substituted or unsubstituted C2-C20 acylamino, substituted or unsubstituted C2-C20 alkoxycarbonylamino, substituted or unsubstituted C7-C20 aryloxycarbonylamino, substituted or unsubstituted C1-C20 sulfamoylamino, substituted or unsubstituted C1-C20 sulfonyl, substituted or unsubstituted C1-C20 sulfanyl, substituted or unsubstituted C1-C20 substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 sulfanyl, substituted or unsubstituted C1-C20 phenylthio, and substituted or unsubstituted phenyl ring;
x is independently selected from anionic groups.
Preferably, the chromium compound is selected from chromium dichloride, chromium dibromide, chromium diacetate or dinitrochromium.
Preferably, the molar ratio of the ligand with the structure of formula (II) to chromium in the chromium compound is 1:1-2.
The application also provides a preparation method of the multi-block polyester material, which comprises the following steps:
epoxide and CO under the action of catalyst and promoter 2 And cyclic ester to obtain multi-block polyester material with a structure shown in a formula (VIII);
the catalyst is the chromium compound or the chromium compound prepared by the preparation method;
the Q is selected from
a is 1,2, 3 or 4; x is 4, 5 or 6; m is more than or equal to 5 and less than or equal to 50; n is more than or equal to 5 and less than or equal to 50;
the R is 9 Selected from-H or C 1 ～C 4 Alkyl of (C), R is 10 Selected from C 1 ～C 5 Alkyl, C of (2) 1 ～C 4 Haloalkyl, C 2 ～C 6 Alkenyl, C 3 ～C 8 Alkenyl ethers of C 3 ～C 8 Alkynyl ether, phenyl or substituted phenyl.
Preferably, the cocatalyst is selected from one or more of bis (triphenylphosphine) ammonium chloride, 4-dimethylaminopyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, N-methylimidazole, tricyclohexylphosphine, tetrabutylammonium chloride and tetrabutylammonium bromide.
Preferably, the molar ratio of the catalyst to the cocatalyst is 1 (0.5-2); the molar ratio of the total number of moles of catalyst and cocatalyst to the moles of cyclic ester, epoxide is 1: (50-1000): (100-5000).
Preferably, the pressure of the carbon dioxide is 0.5-5 MPa; the temperature of the copolymerization reaction is 60-120 ℃; the time of the copolymerization reaction is 0.5-48 h.
The invention provides a chromium compound, which has a structure shown in a formula (I); the chromium compound provided by the invention is formed by chelating metal chromium with a ligand containing a Schiff base bond and a catalyst structure, and has catalytic performance which shows special catalytic performance compared with complexes such as Schiff base chromium and the like: catalytic epoxide and CO 2 The copolymerization reaction can maintain excellent catalytic activity and high polycarbonate segment selectivity in a wider range; the experimental results show that: catalytic epoxide and CO using chromium compounds 2 And epsilon-caprolactone ternary polymerization reaction to obtain multi-block with molecular weight up to 45kDaA segmented polyester material.
Drawings
FIG. 1 is a cyclohexane oxide/CO prepared in example 9 of the present invention 2 Structural characterization of epsilon-caprolactone multiblock copolymer.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The embodiment of the invention discloses a chromium compound, which has a structure shown in a formula (I):
wherein R is 1 ～R 8 Each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, hydroxy, nitro, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C3-C40 siloxy, substituted or unsubstituted C1-C20 acyl, substituted or unsubstituted C2-C20 alkoxycarbonyl, substituted or unsubstituted C2-C20 acyloxy, substituted or unsubstituted C2-C20 acylamino, substituted or unsubstituted C2-C20 alkoxycarbonylamino, substituted or unsubstituted C7-C20 aryloxycarbonylamino, substituted or unsubstituted C1-C20 sulfamoylamino, substituted or unsubstituted C1-C20 sulfonyl, substituted or unsubstituted C1-C20 sulfanyl, substituted or unsubstituted C1-C20 substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 sulfanyl, substituted or unsubstituted C1-C20 phenylthio, and substituted or unsubstituted phenyl ring;
x is independently selected from anionic groups.
According to the invention, more particularly R 1 ～R 8 Each independently selected from hydrogen, halogen, cyano, hydroxy, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxy; more specifically, R 1 ～R 8 Each independently selected from-H, -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 F, -Cl, -Br or-NO 2 。
In a specific embodiment, said R 2 、R 4 、R 6 And R is 8 Are all selected from hydrogen, R is 1 、R 3 、R 5 And R is 7 Each independently selected from t-butyl, methyl or hydrogen.
The X is selected from F, cl, br, I, NO 3 、CH 3 COO、CCl 3 COO、CF 3 COO、ClO 4 P-methylbenzoate, p-toluenesulfonate, 2, 4-dinitrophenol oxygen, 3, 5-dinitrophenol oxygen, p-nitrophenol oxygen or o-nitrophenol oxygen.
The invention provides a preparation method of a chromium compound, which comprises the following steps:
a) Reacting a compound having the structure of formula (VI) with a compound having the structure of formula (VII) to obtain a compound having the structure of formula (V);
b) Removing Boc protecting groups from the compound with the structure of formula (V) under the action of trifluoroacetic acid to obtain a compound with the structure of formula (III);
c) Reacting a compound with a structure of formula (III) with a substituted salicylaldehyde with a structure of formula (IV) to obtain a ligand with a structure of formula (II);
d) Reacting a ligand with a structure shown in a formula (II) with a chromium compound in a solvent to obtain a chromium compound with a structure shown in a formula (I);
wherein R is 1 ～R 8 Each independently selected from hydrogen, deuterium, halogen, cyano, hydroxy, nitro, substituted or unsubstituted C1-C20Substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C1 to C20 alkoxycarbonylamino, substituted or unsubstituted C1 to C20 sulfamoylamino, substituted or unsubstituted C1 to C20 sulfonyl, substituted or unsubstituted C1 to C20 alkylthio, substituted or unsubstituted C6 to C20 arylthio, substituted or unsubstituted C2 to C20 acyloxy, substituted or unsubstituted C2 to C20 acylamino, substituted or unsubstituted C2 to C20 alkoxycarbonylamino, substituted or unsubstituted C7 to C20 arylcarbonylamino, substituted or unsubstituted C1 to C20 sulfamoylamino, substituted or unsubstituted C1 to C20 sulfonyl, substituted or unsubstituted C1 to C20 alkylthio, substituted or unsubstituted C6 to C20 arylthio, substituted or unsubstituted C1 to C20 heterocycle, substituted or unsubstituted C1 to C20 phenylthio, and any two or more fused rings formed with substituted or unsubstituted C1 to C20 phenylthio;
x is independently selected from anionic groups.
The ligand with the structure shown in the formula (II) and the chromium compound are used as raw materials, and the ligand with the structure shown in the formula (II) and the chromium compound react in a solvent to obtain the chromium compound with the structure shown in the formula (I).
The invention takes a semi-amine compound with a structure shown in a formula (III) and substituted salicylaldehyde with a structure shown in a formula (IV) as raw materials, and the semi-amine compound with the structure shown in the formula (III) and the substituted salicylaldehyde with the structure shown in the formula (IV) are reacted in an organic solvent to obtain the ligand with the structure shown in the formula (II).
The invention uses the compound with the structure of formula (V) to remove Boc protecting group under the action of trifluoroacetic acid to obtain the compound with the structure of formula (III).
The invention takes a compound with a structure of a formula (VI) and a compound with a structure of a formula (VII) as raw materials, and the compound with a structure of a formula (V) is obtained by reacting the raw materials in an organic solvent.
In the present invention, the organic solvent is preferably an alcohol solvent, a hydrocarbon solvent, an aromatic solvent, a halogenated hydrocarbon solvent, or the like. The chromium compound is selected from chromium dichloride, chromium dibromide, chromium diacetate or dinitrochromium. The molar ratio of the ligand with the structure shown in the formula (II) to the chromium in the chromium compound is 1:1-2.
The invention provides a chromium compound catalytic epoxide and CO 2 A method for preparing a multi-block polyester material by copolymerization with a cyclic ester, comprising the steps of:
epoxide and CO under the action of catalyst and promoter 2 Reacting with cyclic ester to obtain a reaction product;
the catalyst is the chromium compound disclosed in the technical scheme or the chromium compound obtained by the preparation method disclosed in the technical scheme.
The invention uses epoxide and CO 2 And reacting with cyclic ester under the action of a catalyst and a cocatalyst to obtain the multi-block polyester material, wherein the catalyst is the chromium compound according to the technical scheme or the chromium compound obtained by the preparation method according to the technical scheme.
In the present invention, the catalytic epoxide, CO 2 The copolymerization reaction with the cyclic ester is preferably carried out under anhydrous and anaerobic conditions, preferably epoxide, cyclic ester, catalyst and cocatalyst are mixed and added into a high-pressure reaction kettle which is dehydrated and deoxidized at high temperature, and then carbon dioxide is introduced into the high-pressure reaction kettle for carrying out the reaction.
In the present invention, the epoxide is preferably one or more of ethylene oxide, propylene oxide, cyclohexane oxide, cyclopentane oxide, styrene oxide, epichlorohydrin and neopentyl glycol diglycidyl ether, more preferably one or more of ethylene oxide, propylene oxide and cyclohexane oxide.
In the present invention, the cocatalyst is selected from one or more of bis (triphenylphosphine) ammonium chloride (PPNCl), 4-Dimethylaminopyridine (DMAP), N-methylimidazole, tricyclohexylphosphine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, tetrabutylammonium chloride and tetrabutylammonium bromide, more preferably one or both of PPNCl and DMAP, and most preferably PPNCl.
In the present invention, the molar ratio of the chromium compound to the cocatalyst is preferably 1 (0.5 to 2); the molar ratio of the total number of moles of catalyst and cocatalyst to the moles of cyclic ester, epoxide is preferably 1: (50-1000): (100-5000).
In the present invention, the pressure of the carbon dioxide is preferably 0.5MPa to 5MPa.
In the invention, the temperature of the copolymerization reaction is 60-120 ℃; in the present invention, the time for the copolymerization reaction is 0.5 to 48 hours.
The structural formula of the multi-block polyester material prepared by the invention is shown as follows:
the Q is selected from
a is 1,2, 3 or 4; x is 4, 5 or 6; m is more than or equal to 5 and less than or equal to 50; n is more than or equal to 5 and less than or equal to 50;
the R is 9 Selected from-H or C 1 ～C 4 Alkyl of (C), R is 10 Selected from C 1 ～C 5 Alkyl, C of (2) 1 ～C 4 Haloalkyl, C 2 ～C 6 Alkenyl, C 3 ～C 8 Alkenyl ethers of C 3 ～C 8 Alkynyl ether, phenyl or substituted phenyl.
Preferably, R 9 Selected from-H, R 10 Selected from-CH 3 、-CH 2 Cl or phenyl.
The invention provides a chromium compound, which has a structure shown in a formula (I). The chromium complex provided by the invention is formed by chelating metal chromium with a ligand with a half Schiff base and cath structure, and has catalytic performance which shows special catalytic performance compared with the complex such as Schiff base chromium and the like: catalytic epoxycyclohexane and CO 2 The copolymerization reaction can maintain excellent catalytic activity and high polycarbonate segment selectivity in a wider range; can catalyze epoxide and CO by a one-pot one-step method 2 And cyclic ester to obtainTo multiblock polymer, the chain segment proportion can be adjusted by adjusting the monomer feeding proportion, the reaction temperature, the reaction pressure and the like. Experimental results show that the chromium compound is used for catalyzing the epoxy cyclohexane and CO 2 And epsilon-caprolactone ternary polymerization reaction to obtain the multi-block polyester material with molecular weight of 45kDa.
In order to further understand the present invention, the chromium compounds, the preparation method thereof and the application thereof provided by the present invention are described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
22.2g of 3, 5-di-tert-butylphenyl-o-diphenol and 21.4g of 1-N-Boc-1, 2-cyclohexanediamine were added to 300mL of N-hexane, and after stirring at room temperature for 72 hours, the solid was collected by filtration to give compound (V).
The yield of compound (V) calculated in the present invention was 80%.
The present invention analyzes the compound (V) obtained in this example by nuclear magnetic resonance to obtain a hydrogen spectrum thereof, and the result shows that: 1 H NMR(300MHz，CDCl 3 )：δ＝6.99(1H),6.83(1H),4.53(1H),3.51(2H),2.74(1H),2.14(2H),1.79(2H),1.46(9H),1.42(9H),1.31(9H),1.22(4H)。
the present invention uses a mass spectrometer to analyze the compound (V) obtained in this example, and the results show that: MALDI-TOF, m/z=418.3;
as can be seen from the above results of the NMR hydrogen spectrum and mass spectrometry, the compound prepared in this example has the structure shown in formula (V) wherein R 1 And R is 3 Are all tert-butyl groups.
Example 2
20.9g of the compound (V) obtained in example 1 was dissolved in 300mL of methylene chloride, then 20mL of trifluoroacetic acid was slowly added dropwise in an inert atmosphere, the solvent was removed by rotary evaporation after stirring at room temperature for 2 hours, and after the obtained solid was dissolved in methylene chloride, 0.5M aqueous sodium hydroxide solution was added dropwise to pH=7, and the organic phase, na was collected by extraction 2 SO 4 Drying and rotary steaming to remove the solvent to obtain the compound (III).
The yield of compound (III) calculated in the present invention was 95%.
The invention analyzes the compound (III) obtained in the embodiment by nuclear magnetic resonance to obtain a hydrogen spectrum thereof, and the result shows that: 1 H NMR(300MHz，CDCl 3 )：δ＝7.03(1H),6.79(1H),2.77(2H),2.19(1H),1.97(1H),1.74(2H),1.46(9H),1.31(9H),1.22(4H)。
the present invention uses a mass spectrometer to analyze the compound (III) obtained in this example, and the results show that: MALDI-TOF, m/z=318.3;
as can be seen from the above results of the NMR hydrogen spectrum and mass spectrometry, the compound prepared in this example has the structure shown in formula (III) wherein R 1 And R is 3 Are all tert-butyl groups.
Example 3
3.18g of the compound (III) obtained in example 2 and 2.34g of 3, 5-di-t-butylsalicylaldehyde were added to 50nL of methanol, stirred at room temperature for 24 hours, and the solid was collected by filtration to obtain the ligand (II).
The yield of compound (II) calculated in the present invention was 68%.
The ligand (II) obtained in the embodiment is analyzed by nuclear magnetic resonance to obtain a hydrogen spectrum, and the result shows that: 1 H NMR(300MHz，CDCl 3 )：δ＝13.55(1H),8.51(1H),7.40(1H),7.13(1H),7.04(1H),6.97(1H),3.05(2H),2.64(1H),2.03(2H),1.88(2H),1.47(9H),1.36(9H),1.32(9H),1.29(9H),1.24(4H)。
the present invention uses a mass spectrometer to analyze the ligand (II) obtained in this example, and the result shows that: MALDI-TOF, m/z= 534.4;
as can be seen from the above results of the NMR hydrogen spectrum and mass spectrometry, the compound prepared in this example has the structure shown in formula (II) wherein R 1 、R 3 、R 5 And R is 7 Are all tert-butyl groups.
Example 4
The ligand is prepared by adopting the technical scheme of the embodiment 3, and the difference is that: this example uses 3, 5-dimethyl salicylaldehyde instead of 3, 5-di-tert-butyl salicylaldehyde as in example 3.
The invention carries out nuclear magnetic resonance hydrogen spectrum analysis, mass spectrum analysis and meta-analysis on the obtained reaction productThe results of the plain analysis indicate that the ligand prepared in this example has the structure shown in formula (II) wherein R 1 And R is 3 Is tert-butyl, R 5 And R is 7 Is methyl.
Example 5
The ligand is prepared by adopting the technical scheme of the embodiment 3, and the difference is that: this example uses 3-tert-butylsalicylaldehyde instead of 3, 5-di-tert-butylsalicylaldehyde as in example 3.
The obtained reaction product is subjected to nuclear magnetic resonance hydrogen spectrum analysis, mass spectrum analysis and element analysis, and the result shows that the ligand prepared in the embodiment has the structure shown in the formula (II), wherein R 1 And R is 3 Is tert-butyl, R 5 Is tert-butyl, R 7 Is hydrogen.
Example 6
Under nitrogen atmosphere, 0.534g of the ligand prepared in example 3 and 0.123g of chromium dichloride were dissolved in 20mL of THF, and the mixture was stirred at room temperature to react for 12 hours and then exposed to air for oxidation for 12 hours. 100mL diethyl ether dilution reaction system, saturated ammonium chloride solution, saturated saline solution washing organic phase, na 2 SO 4 The organic phase was dried and the solvent was removed by rotary evaporation to give chromium compound (I).
The present invention calculated 94% yield of chromium compound.
The invention uses a mass spectrometer to analyze the chromium compound obtained in the embodiment, and the result shows that: ESI-MS, m/z= 584.3 (-Cl).
As shown by the analysis results, the chromium compound prepared in the present example has a structure represented by the formula (I) wherein R 1 、R 3 、R 5 And R is 7 Are all tert-butyl groups.
Example 7
The chromium compound was prepared by the technical scheme of example 6, except that the ligand obtained in example 4 was used in this example instead of the ligand prepared in example 3 used in example 6.
The obtained reaction product is subjected to nuclear magnetic resonance analysis and mass spectrometry, and the result shows that the chromium compound obtained in the embodiment has the structure shown in the formula (I), wherein R 1 And R is 3 Is tert-butyl, R 5 And R is 7 Is methyl.
Example 8
The chromium compound was prepared by the technical scheme of example 6, except that the ligand obtained in example 4 was used in this example instead of the ligand prepared in example 3 used in example 6.
The obtained reaction product is subjected to nuclear magnetic resonance analysis and mass spectrometry, and the result shows that the chromium compound obtained in the embodiment has the structure shown in the formula (I), wherein R 1 And R is 3 Is tert-butyl, R 5 Is tert-butyl, R 7 Is hydrogen.
Example 9
1.58g of epoxycyclohexane, 0.5g of epsilon-caprolactone, 0.023g of the chromium compound obtained in example 6 and 0.02g of PPNCl promoter are added into a high-pressure reactor which is dehydrated at high temperature, and CO of 2MPa is charged 2 And reacted at 80℃for 6h. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed that the conversion of epoxycyclohexane was 74% and the conversion of epsilon-caprolactone was 64%, and the reaction products were all polycarbonate and polyester; the obtained polymer is proved to contain CO by adopting two-dimensional nuclear magnetic spectrum chart characterization 2 -epsilon-caprolactone linkage and epsilon-caprolactone-epoxycyclohexane linkage, demonstrating that this three-component polymerization gives a multi-block copolymer (as shown in figure 1); the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 18kDa.
Example 10
1.58g of epoxycyclohexane, 0.5g of epsilon-caprolactone, 0.023g of the chromium compound obtained in example 6 and 0.02g of PPNCl promoter are added into a high-pressure reactor which is dehydrated at high temperature, and CO of 1MPa is charged 2 And reacted at 100℃for 3 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed 68% conversion of epoxycyclohexane and 87% conversion of epsilon-caprolactone, with all of the reaction products being polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 15kDa.
Example 11
3.16g of epoxycyclohexane, 0.5g of epsilon-caprolactone, 0.023g of the chromium compound obtained in example 6 and 0.03g of PPNCl promoter are added into a high-pressure reaction kettle which is dehydrated at high temperature, and CO of 2MPa is charged 2 And reacted at 80℃for 10 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed 59% conversion of epoxycyclohexane and 34% conversion of epsilon-caprolactone, with all of the reaction products being polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 17kDa.
Example 12
1.58g of epoxycyclohexane, 0.5g of epsilon-caprolactone, 0.021g of the chromium compound obtained in example 7 and 0.02g of PPNCl promoter were charged into a high-pressure reactor which had been dehydrated at high temperature, and 2MPa of CO was charged 2 And reacted at 80℃for 6h. The reaction vessel was then cooled to room temperature, releasing the residual gases. The product was dissolved in 5ml of dichloromethane to giveSlowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed 62% conversion of epoxycyclohexane and 68% conversion of epsilon-caprolactone, with all of the reaction products being polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 14kDa.
Example 13
1.58g of epoxycyclohexane, 0.5g of epsilon-caprolactone, 0.019g of the chromium compound obtained in example 8 and 0.01g of DMAP promoter were charged into a high-pressure reactor which had been dehydrated at high temperature, and CO of 2MPa was charged 2 And reacted at 80℃for 8 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed that the conversion of epoxycyclohexane was 78% and the conversion of epsilon-caprolactone was 68%, and the reaction products were all polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 15kDa.
Example 14
2.21g of epoxycyclohexane, 0.58g of epsilon-caprolactone, 0.020g of chromium compound obtained in example 6 and 0.008g of DMAP promoter were charged into a high-pressure reactor which had been dehydrated at high temperature and charged with 2MPa of CO 2 And reacted at 100℃for 5 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; dissolving the precipitated polymer with dichloromethane again, and precipitating in ethanolDrop, repeat 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed 65% conversion of epoxycyclohexane and 59% conversion of epsilon-caprolactone, with all of the reaction products being polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 23kDa.
Example 15
1.58g of epoxycyclohexane, 0.18g of epsilon-caprolactone, 0.020g of chromium compound obtained in example 6 and 0.02g of PPNCl promoter were charged into a high-pressure reactor which had been dehydrated at high temperature and charged with CO at 0.5MPa 2 And reacted at 90℃for 4 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed that the conversion of epoxycyclohexane was 76% and the conversion of epsilon-caprolactone was 76%, and the reaction products were all polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 17kDa.
Example 16
2.35g of epoxycyclohexane, 0.5g of epsilon-caprolactone, 0.021g of the chromium compound obtained in example 7 and 0.018g of PPNCl promoter were charged into a high-pressure reactor which had been dehydrated at high temperature, and CO of 2MPa was charged 2 And reacted at 100℃for 18h. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention can obtainThe reaction solution is subjected to 1 H-NMR analysis showed that the conversion of epoxycyclohexane was 79% and the conversion of epsilon-caprolactone was 86%, and the reaction products were all polycarbonates and polyesters; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 45kDa.
Example 17
1.58g of epoxycyclohexane, 0.37g of epsilon-caprolactone, 0.019g of the chromium compound obtained in example 8 and 0.02g of PPNCl promoter are added into a high-pressure reactor which is dehydrated at high temperature, and CO of 2MPa is charged 2 And reacted at 50℃for 6 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed 58% conversion of epoxycyclohexane and 0% conversion of epsilon-caprolactone, with all of the reaction products being polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 14kDa.
Example 18
1.58g of epoxycyclohexane, 0.8g of epsilon-caprolactone, 0.021g of the chromium compound obtained in example 8 and 0.019g of PPNCl promoter were charged into a high-pressure reactor which had been dehydrated at high temperature, and CO of 2MPa was charged 2 And reacted at 80℃for 3 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed that the conversion of epoxycyclohexane was 52%, the conversion of ε -caprolactone was 12%, and the reaction product was allThe parts are polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 14kDa.
Example 19
1.35g of cyclopentane epoxide, 0.36g of epsilon-caprolactone, 0.019g of the chromium compound obtained in example 6 and 0.02g of PPNCl promoter were charged into a high-pressure reactor which had been dehydrated at high temperature, and CO of 2MPa was charged 2 And reacted at 80℃for 12h. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed 58% conversion of cyclopentane epoxide and 46% conversion of epsilon-caprolactone, with all of the reaction products being polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 13kDa.
Example 20
1.58g of epoxycyclohexane, 0.25g of delta-valerolactone, 0.019g of the chromium compound obtained in example 7 and 0.008g of DMAP promoter were charged into a high-pressure reactor which was dehydrated at high temperature, and 1MPa of CO was charged 2 And reacted at 100℃for 6 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed that the conversion of epoxycyclohexane was 76% and the conversion of delta-valerolactone was 12%, and the reaction products were all polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 14kDa。
Example 21
1.58g of epoxycyclohexane, 0.19g of epsilon-caprolactone, 0.020g of the chromium compound obtained in example 7 and 0.019g of PPNCl promoter were charged into a high-pressure reactor which had been dehydrated at high temperature, and 4MPa of CO was charged 2 And reacted at 80℃for 5 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis showed 57% conversion of epoxycyclohexane and 52% conversion of epsilon-caprolactone, with all of the reaction products being polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 15kDa.
Example 22
1.32g of cyclopentane epoxide, 0.16g of delta-valerolactone, 0.020g of the chromium compound obtained in example 6 and 0.019g of PPNCl cocatalyst were charged into a high-pressure reactor which had been dehydrated at high temperature, and CO was charged under 1MPa 2 And reacted at 100℃for 5 hours. The reaction vessel was then cooled to room temperature, releasing the residual gases. Dissolving the product with 5ml of dichloromethane, slowly dripping the obtained solution into 500ml of ethanol, stirring for 15min, and standing for 30min; the precipitated polymer was dissolved again with dichloromethane, precipitated in ethanol and repeated 3 times. And (5) drying the solid obtained by sedimentation in vacuum to obtain a reaction product.
The invention carries out the reaction liquid 1 H-NMR analysis shows that the conversion rate of cyclopentane epoxide is 38%, the conversion rate of delta valerolactone is 8%, and all reaction products are polycarbonate and polyester; the copolymer obtained in this example was analyzed by gel permeation chromatography to give a polyester having a number average molecular weight of 6kDa.
From the above examples, the present invention provides a chromium compound having a structure represented by formula (I). The book is provided withThe invention reacts with a ligand with a structure shown in a formula (II) and a chromium compound to obtain the chromium compound with the structure shown in the formula (I). The method combines the obtained chromium compound with the cocatalyst to catalyze the epoxide and the CO 2 And the copolymerization of the cyclic ester to obtain the multi-block polyester material. The chromium compound provided by the invention catalyzes epoxide and CO 2 The copolymerization reaction can maintain excellent catalytic activity and high polycarbonate segment selectivity in a wider range; can catalyze epoxide and CO by a one-pot one-step method 2 And the cyclic ester is subjected to ternary polymerization reaction to obtain a multiblock polymer, and the proportion of chain segments can be adjusted by adjusting the monomer feeding proportion, the reaction temperature, the reaction pressure and the like. The experimental results show that: the chromium compound is adopted to catalyze the epoxy cyclohexane and CO 2 And epsilon-caprolactone ternary polymerization reaction to obtain the multi-block polyester material with molecular weight of 45kDa.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A chromium compound having a structure represented by formula (I):
wherein R is 1 、R 3 Is tert-butyl, R 5 、R 7 Independently selected from hydrogen, methyl or t-butyl, R 2 、R 4 、R 6 、R 8 Is hydrogen and X is Cl.
2. A process for the preparation of a chromium compound according to claim 1, comprising the steps of:
a) Reacting a compound having the structure of formula (VI) with a compound having the structure of formula (VII) to obtain a compound having the structure of formula (V);
b) Removing Boc protecting groups from the compound with the structure of formula (V) under the action of trifluoroacetic acid to obtain a compound with the structure of formula (III);
c) Reacting a compound with a structure of formula (III) with a substituted salicylaldehyde with a structure of formula (IV) to obtain a ligand with a structure of formula (II);
d) Reacting a ligand with a structure shown in a formula (II) with a chromium compound in a solvent to obtain a chromium compound with a structure shown in a formula (I);
wherein R is 1 、R 3 Is tert-butyl, R 5 、R 7 Independently selected from hydrogen, methyl or t-butyl, R 2 、R 4 、R 6 、R 8 Is hydrogen and X is Cl.
3. The method of claim 2, wherein the chromium compound is selected from the group consisting of chromium dichloride, chromium dibromide, chromium diacetate, and dinitrochromium.
4. The preparation method according to claim 2, wherein the molar ratio of the ligand having the structure of formula (II) to chromium in the chromium compound is 1:1-2.
5. A method for preparing a multi-block polyester material, comprising the steps of:
epoxide and CO under the action of catalyst and promoter 2 And cyclic ester to obtain multi-block polyester material with a structure shown in a formula (VIII); the epoxide is selected from cyclohexane oxide or cyclopentane oxide, and the cyclic ester is selected from epsilon-caprolactone or delta-valerolactone;
the catalyst is the chromium compound of claim 1 or the chromium compound prepared by the preparation method of any one of claims 2 to 4;
the cocatalyst is selected from bis (triphenylphosphine) ammonium chloride or 4-dimethylaminopyridine;
the Q is selected from
a is 1 or 2; x is 4 or 5; m is more than or equal to 5 and less than or equal to 50; n is more than or equal to 5 and less than or equal to 50.
6. The process according to claim 5, wherein the molar ratio of catalyst to cocatalyst is 1 (0.5-2); the molar ratio of the total number of moles of catalyst and cocatalyst to the moles of cyclic ester, epoxide is 1: (50-1000): (100-5000).
7. The method according to claim 5, wherein the pressure of the carbon dioxide is 0.5 to 5MPa; the temperature of the copolymerization reaction is 60-120 ℃; the time of the copolymerization reaction is 0.5-48 h.
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| CO2Controlled Catalysis: Switchable Homopolymerization and Copolymerization;Chenyang Hu et al.,;Macromolecules;第51卷;4699-4704 * |
| Switch Catalysis To Deliver Multi-Block Polyesters from Mixtures of Propene Oxide, Lactide, and Phthalic Anhydride;Tim Stober et al.,;Communications;第57卷(第16893-16897期);16893-16897 * |
| 选择性催化混合单体制备多组分聚酯的研究进展;周延川等，;中国科学：化学;第51卷(第2期);144-153 * |
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