CN108047432B - Method for catalyzing caprolactone polymerization by using asymmetric aluminum complex containing acetylacetone derivative - Google Patents
Method for catalyzing caprolactone polymerization by using asymmetric aluminum complex containing acetylacetone derivative Download PDFInfo
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- CN108047432B CN108047432B CN201711314947.XA CN201711314947A CN108047432B CN 108047432 B CN108047432 B CN 108047432B CN 201711314947 A CN201711314947 A CN 201711314947A CN 108047432 B CN108047432 B CN 108047432B
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 63
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 30
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 154
- 239000003446 ligand Substances 0.000 claims abstract description 94
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 22
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 14
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 66
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 62
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 56
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 44
- 238000005406 washing Methods 0.000 claims description 28
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 41
- 239000000047 product Substances 0.000 description 41
- 238000001035 drying Methods 0.000 description 29
- 239000007787 solid Substances 0.000 description 25
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- -1 cyclic lactone Chemical class 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000003708 ampul Substances 0.000 description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- VVXLFFIFNVKFBD-UHFFFAOYSA-N 4,4,4-trifluoro-1-phenylbutane-1,3-dione Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CC=C1 VVXLFFIFNVKFBD-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for catalyzing caprolactone polymerization by using an asymmetric aluminum complex containing an acetylacetone derivative, which comprises the following steps: mixing a catalyst, an organic solvent, a benzyl alcohol cocatalyst and caprolactone, carrying out ring-opening polymerization reaction under the protection of anhydrous, oxygen-free and inert gases, and processing reactants after reaction to obtain polycaprolactone; the catalyst is an asymmetric aluminum complex containing acetylacetone derivatives. The asymmetric aluminum complex containing the acetylacetone derivative is used as the catalyst to carry out the caprolactone ring-opening polymerization reaction, the preparation method of the asymmetric aluminum complex containing the acetylacetone derivative is simple, the cost is low, the product yield is high, the catalyst structure is varied, the divalent N, N, O and O of metal center aluminum and ligand are coordinated, the catalytic activity is high, the stereoselectivity is high, the reaction rate is high, the obtained polymerization product is a benzyloxy-terminated polymer, the molecular weight distribution is narrow, the molecular weight is controllable, the yield is high, and the market demand is met.
Description
Technical Field
The invention relates to a method for catalyzing caprolactone polymerization, in particular to a method for catalyzing caprolactone polymerization by using an asymmetric aluminum complex containing an acetylacetone derivative.
Background
Traditional plastics made from petroleum have several advantages, but have two fatal disadvantages: non-regenerability and non-degradability. Under the condition that petroleum is exhausted as a non-renewable resource, the rapid development of high polymer materials depending on petroleum raw materials is greatly restricted, the high polymer materials are difficult to degrade, and the pollution to human living environment caused by long-term accumulation of a large amount of high polymer material wastes in real life is gradually increased. It is therefore highly desirable to find renewable resources to replace petroleum.
Because polyester is non-toxic, non-irritant and has good biocompatibility, polyester is a biodegradable green environment-friendly high polymer material, and polyester materials are more and more concerned as substitutes of petroleum products. In a natural living environment, the waste polylactone material can be thoroughly decomposed into water and carbon dioxide by microorganisms in soil, is environment-friendly and is renewable. Polyesters are widely used in medical and environmental fields, such as surgical sutures, packaging, drug controlled release and tissue engineering scaffolds, etc. The excellent biocompatibility, biodegradability and sustainable development and utilization performance of the polylactone make the polylactone become a polymer material with the greatest development prospect in the 21 st century.
A convenient method for synthesizing polyester is a ring-opening polymerization method of cyclic lactone, and the synthesis method has the advantages that: controllability of polymerization, narrower molecular weight distribution. At present, most of commonly used catalysts are complexes formed by ligands and metals, in the metal complex catalysts, the selection of the ligands and the selective catalysts of the metals is very critical to the speed of ring-opening polymerization reaction and the performance of the obtained products, under the condition of the same metal, the replacement and selection of the ligands often show unexpected catalytic effects, and under the condition of the same ligand, the replacement of the metals can also generate different catalytic effects, so that the research of new catalysts with good performance is very necessary.
Disclosure of Invention
The invention provides a method for catalyzing caprolactone polymerization by using an asymmetric aluminum complex containing an acetylacetone derivative, which is simple to operate, good in reaction controllability and high in yield, and takes a self-developed asymmetric aluminum complex containing the acetylacetone derivative as a catalyst, and the molecular weight of the obtained polycaprolactone is controllable.
The invention is completed under the subsidization of the national Natural fund Commission youth project (No 21104026), and the technical scheme of the invention is as follows:
the invention provides an asymmetric aluminum complex catalyst containing acetylacetone derivatives with a special structure, which has a structural formula shown as the following formula (I):
the asymmetric aluminum complex containing the acetylacetone derivative has excellent performance through the selection of a ligand structure and the coordination with metallic aluminum, and the selection of a substituent group in the ligandThe aluminum complex has great influence on the catalytic performance of the catalyst for the ring-opening polymerization reaction of the cyclic lactone. Wherein R is1Is trifluoromethyl or methyl, R2Excellent catalytic performance when it is phenyl, trifluoromethyl or methyl, R1、R2May be the same or different. Further, from the aspects of steric hindrance, electron cloud density and the like, the strong electron-withdrawing group (trifluoromethyl) can improve the catalytic activity of the aluminum complex when R is1Is trifluoromethyl, R2The catalytic activity is higher when the compound is trifluoromethyl.
The asymmetric aluminum complex catalyst containing the acetylacetone derivative is obtained by reacting a ligand with trimethylaluminum, and the preparation method comprises the following steps: adding the ligand A into an organic solvent, and then adding the ligand A into the organic solvent at-10 to 0 DEG CoAnd C, adding trimethylaluminum, naturally raising the reaction temperature to room temperature, heating for reaction, and performing vacuum drying, washing and filtering on the reaction mixture to obtain the asymmetric aluminum complex containing the acetylacetone derivative.
The formula of the reaction of the ligand A and trimethylaluminum is shown as follows, wherein the structural formula of the ligand A is shown as the following formula, R1Is trifluoromethyl or methyl, preferably trifluoromethyl; r2Is phenyl, trifluoromethyl or methyl, preferably trifluoromethyl:
in the above preparation method, the preparation method of the ligand A comprises the following steps: dissolving p-toluenesulfonic acid in dimethylbenzene, slowly adding ethylenediamine with the same molar amount as the p-toluenesulfonic acid, adding phthalic anhydride with the same molar amount as the p-toluenesulfonic acid, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering to obtain a solid, dissolving the obtained solid in dichloromethane, slowly dropwise adding an excessive saturated sodium bicarbonate aqueous solution to remove the p-toluenesulfonic acid, separating the liquid after the reaction is finished, drying the obtained organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain ethylenediamine protected by unilateral phthalic anhydride; ethylenediamine protected with single-sided phthalic anhydrideDissolving the acetylacetone derivative with equimolar amount in methanol, heating for reflux reaction, cooling and filtering after the reaction is finished, and washing and drying the obtained solid with cold methanol to obtain a ligand A; the structural formula of the acetylacetone derivative is shown as the following formula B, wherein R1Is trifluoromethyl or methyl, preferably trifluoromethyl, R2Is phenyl, trifluoromethyl or methyl, preferably trifluoromethyl.
In the above preparation method, the ligand a and trimethylaluminum undergo an addition reaction, and the methyl group of trimethylaluminum is added to the C = O double bond in the ligand a, and the C = O double bond is changed to a C — O single bond. Is found in by nuclear magnetic characterizationIn the range of = 1.5-2.0, there is a group of CH3The characteristic peak of (A) is NC (O) (Ar) CH 3Middle CH3Characteristic peak of (2).
In the preparation method, the molar ratio of the ligand A to the trimethylaluminum is 1: 1 to 1.3, preferably 1: 1 to 1.05.
In the above preparation method, the organic solvent is one or two of dried hexane, toluene and cyclohexane, and is preferably dried hexane or toluene.
In the preparation method, the dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials (the ligand A and the trimethylaluminum).
In the preparation method, the reaction is carried out under the protection of gas, and the gas is inert gas or nitrogen.
In the preparation method, the reaction is naturally raised to room temperature and then raised to 30-110 DEG CoC by reaction, e.g. 30oC、40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC, preferably 40 to 60oC. In the range of 30 to 110oC (preferably 40-60)oC) The reaction time is 1 to 12 hours, preferably 3 to 6 hours. After the reaction, the precipitate was washed with n-hexane.
The asymmetric aluminum complex containing the acetylacetone derivative is an intermediate product for preparing the compound shown in the formula II, the asymmetric aluminum complex containing the acetylacetone derivative is sensitive to water, water is added into a reaction liquid obtained after a ligand A and trimethylaluminum react, the mixture is fully stirred to hydrolyze the aluminum complex, and the compound shown in the formula II is obtained after liquid separation, organic phase collection and solvent recovery of the organic phase, and the obtained remainder is recrystallized. Therefore, the preparation of the aluminum complex is carried out in the absence of water and a protic solvent. In addition, the asymmetric aluminum complex containing the acetylacetone derivative in the formula I can be obtained by using the compound in the formula II as a raw material and replacing the ligand A with the compound in the formula II according to the preparation method of the asymmetric aluminum complex containing the acetylacetone derivative.
When the asymmetric aluminum complex containing the acetylacetone derivative is prepared by using the compound shown in the formula II, the organic solvent is one or two of dry hexane, toluene and cyclohexane, and hexane or toluene is preferred. The dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials (the compound and the trimethylaluminum in the formula II). After the reaction is finished, dried hexane is used for recrystallization, and the asymmetric aluminum complex containing the acetylacetone derivative and having high purity is obtained.
The asymmetric aluminum complex containing the acetylacetone derivative is a complex, N, N, O, O of the ligand is coordinated with aluminum, the structure of the complex is very similar to that of a classical cyclic lactone catalyst (salenAl), the catalytic effect is good, the stereoselectivity is high, and the asymmetric aluminum complex is a good catalyst for the ring-opening polymerization reaction of the cyclic lactone.
When the asymmetric aluminum complex containing the acetylacetone derivative is used as a catalyst for the ring-opening polymerization reaction of the cyclic lactone, the ring-opening polymerization of the caprolactone can be catalyzed to obtain a series of polycaprolactone. The invention specifically provides a method for catalyzing caprolactone polymerization by using the asymmetric aluminum complex containing the acetylacetone derivative, which comprises the following steps: mixing an asymmetric aluminum complex catalyst containing acetylacetone derivatives, an organic solvent, a benzyl alcohol cocatalyst and caprolactone, carrying out ring-opening polymerization reaction under the protection of anhydrous, oxygen-free and inert gases, and processing reactants after the reaction to obtain polycaprolactone.
When the asymmetric aluminum complex containing the acetylacetone derivative is used as a catalyst for the ring-opening polymerization reaction of caprolactone, the electron-withdrawing group can ensure that the catalytic activity of the aluminum catalyst is high, and when R is1Is trifluoromethyl, R2The catalyst activity is highest when the compound is trifluoromethyl.
In the ring-opening polymerization reaction, the molar ratio of caprolactone to the asymmetric aluminum complex catalyst containing the acetylacetone derivative is 50-1500: 1, e.g., 50:1, 100: 1. 150:1, 200:1, 300:1, 400:1, 500:1, 600: 1. 800:1, 1000:1, 1200:1, 1500: 1.
in the ring-opening polymerization reaction, the organic solvent used in the reaction is toluene or tetrahydrofuran, and toluene is preferred.
In the ring-opening polymerization reaction, the alcohol co-catalyst is benzyl alcohol. The molar ratio of the benzyl alcohol cocatalyst to the asymmetric aluminum complex catalyst containing the acetylacetone derivative is 1-3: 1.
in the ring-opening polymerization, the polymerization temperature is 20 to 110 ℃ such as 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and 110 ℃. With the increase of the polymerization temperature, the stereoselectivity of the catalyst tends to decrease, and the catalytic activity tends to increase.
In the ring-opening polymerization reaction, the polymerization reaction time is 1 to 60 minutes, for example, 1 minute, 4 minutes, 10 minutes, 30 minutes, 40 minutes, 60 minutes, or the like.
In the ring-opening polymerization reaction, cold methanol or ethanol is added to purify the polylactone after the reaction, so as to obtain the purified polylactone. The molecular weight of the obtained polycaprolactone is high in controllability and can be adjusted within the range of 1-16.5 ten thousand.
The asymmetric aluminum complex containing the acetylacetone derivative is used as the catalyst to carry out the caprolactone ring-opening polymerization reaction, the preparation method of the asymmetric aluminum complex containing the acetylacetone derivative is simple, the cost is low, the product yield is high, the catalyst structure is varied, the divalent N, N, O and O of metal center aluminum and ligand are coordinated, the catalytic activity is high, the stereoselectivity is high, the reaction rate is high, the obtained polymerization product is a benzyloxy-terminated polymer, the molecular weight distribution is narrow, the molecular weight is controllable, the yield is high, and the market demand is met.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to be limiting and whose scope is indicated in the claims.
Preparation of one-sided protected ethylenediamine (a)
Dissolving 0.50 g of p-toluenesulfonic acid into xylene, slowly adding ethylenediamine with the equimolar amount of the p-toluenesulfonic acid, adding phthalic anhydride with the equimolar amount of the p-toluenesulfonic acid, heating and refluxing for 8 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying the solid to obtain the solid. Dissolving the solid into dichloromethane, slowly dropwise adding an excessive saturated aqueous solution of sodium bicarbonate to remove p-toluenesulfonic acid, reacting at room temperature, separating liquid after the reaction is finished, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain 0.48 g of unilateral phthalic anhydride protected ethylenediamine with the yield of 87.3%. The reaction formula is as follows:
preparation of an asymmetric ligand (A) containing an acetylacetone derivative
Asymmetric ligand A containing acetylacetone derivative is obtained by condensation reaction of single-side protected ethylenediamine and acetylacetone or its derivative, and the following examples are given for different synthetic ligands A.
Example 1
The structural formula of the synthesized ligand is shown as the formula (A), wherein R1Is methyl; r2The reaction process is as follows: 0.30 g of one-sided protected ethylenediamine (a) and an equimolar amount of acetylacetone plusThe reaction mixture was refluxed in 12 mL of methanol for 12 hours, cooled and filtered after the reaction was completed, washed with cold methanol, filtered, collected, dried and weighed to obtain 0.35 g of a solid with a yield of 81.4%.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is methyl; r2The synthesis of the ligand, which is a methyl group, was successful.
1H NMR (400 MHz, CDCl3)10.85 (s, 1H, OH), 8.03 (d,J= 6.4Hz, 2H,Ar–H), 7.56 (d,J= 6.4Hz, 2H, Ar–H), 5.23 (s, 1H, CH), 4.25 (m, 2H, NCH 2),3.42 (m, 2H, =NCH 2), 2.08 (s, 6H, CH 3). HRESI-MS: m/z cacld. C15H16N2O3[M-H]-;271.1085, found: 271.1090.
Example 2
The structural formula of the synthesized ligand is shown as the formula (A), wherein R1Is methyl; r2Is trifluoromethyl, and the reaction process is as follows: 0.20 g of the mono-edge protected ethylenediamine (a) and an equimolar amount of trifluoroacetylacetone were added to 10mL of methanol, and the mixture was refluxed for 12 hours, cooled and filtered after the completion of the reaction and washed with cold methanol, filtered, collected, dried and weighed to obtain 0.30 g of a solid in 88.2% yield.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is methyl; r2The synthesis of the ligand, trifluoromethyl, was successful.
1H NMR (400 MHz, CDCl3)11.25 (s, 1H, OH), 8.05 (d,J= 6.6 Hz, 2H,Ar–H), 7.58 (d,J= 6.6 Hz, 2H, Ar–H), 5.62 (s, 1H, CH), 4.26 (m, 2H, NCH 2),3.45 (m, 2H, =NCH 2), 2.09 (s, 3H, CH 3)。HRESI-MS: m/z cacld. C15H12F3N2O3F[M-H]-; 325.0802, found: 325.0804.
Example 3
The structural formula of the synthesized ligand is shown as the formula (A), wherein R1Is trifluoromethyl; r2Is phenyl, and the reaction process is as follows: 0.25 g of the mono-edge protected ethylenediamine (a) and an equimolar amount of benzoyltrifluoroacetone were added to 20 mL of methanol, and the mixture was refluxed for 12 hours, cooled and filtered after the completion of the reaction and washed with cold methanol, filtered, collected, dried and weighed to obtain 0.45 g of a solid with a yield of 88.2%.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is trifluoromethyl; r2The synthesis of ligands that are phenyl groups was successful.
1H NMR (400 MHz, CDCl3)12.05 (s, 1H, OH), 8.07 (d,J= 6.8 Hz, 2H,Ar–H), 7.60 (d,J= 6.8 Hz, 2H, Ar–H), 7.56-7.47(m, 3H, Ar–H),7.19 (d,J=6.0 Hz, 2H, Ar–H), 6.47 (s, 1H, CH), 4.34 (m, 2H, NCH 2), 3.92 (m, 2H, =NCH 2)。HRESI-MS: m/z cacld. C20H15F3N2O3[M-H]-; 387.0956, found: 387.0958.
Example 4
The structural formula of the synthesized ligand is shown as the formula (A), wherein R1Is trifluoromethyl; r2Is trifluoromethyl, and the reaction process is as follows: 0.40 g of the single-edge protected ethylenediamine (a) and an equimolar amount of hexafluoroacetylacetone were added to 20 mL of methanol, and the mixture was heated under reflux for 10 hours, cooled and filtered after the completion of the reaction, and washed with cold methanol, filtered, collected, dried, and weighed to obtain 0.66 g of a solid in 82.5% yield.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is trifluoromethyl; r2The synthesis of the ligand, trifluoromethyl, was successful.
1H NMR (400 MHz, CDCl3)12.14 (s, 1H, OH), 8.76 (d,J= 7.0 Hz, 2H,Ar–H), 7.86 (d,J= 7.0 Hz, 2H, Ar–H), 6.10 (s, 1H, CH), 4.62 (m, 2H, NCH 2),3.64 (m, 2H, =NCH 2)。HRESI-MS: m/z cacld. C15H9F6N2O3F[M-H]-; 379.0518, found:379.0520.
Preparation of aluminum complexes (I) from ligand A
The aluminum complex containing the acetylacetone derivative is a complex formed by the elimination of an alkyl group and the addition of an alkyl group between the ligand A and trimethylaluminum, and the reaction formula is as follows.
Example 5
The ligand has the structural formula of formula (A), wherein R1Is methyl; r2The reaction process is as follows: dissolving 0.30 g of ligand A in 10mL of dry toluene under nitrogen atmosphere, adding trimethylaluminum with the molar weight being 1.0 time of that of the ligand A at-10 ℃, heating to 90 ℃ after the reaction temperature naturally rises to room temperature for reaction for 2 hours, vacuumizing the solvent after the reaction is finished, adding dry n-hexane for washing, filtering, collecting, drying and weighing to obtain 0.31 g of solid with the yield of 86.1%.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is methyl; r2The synthesis of the aluminum complex (I) which is methyl is successful.
1H NMR (400 MHz, CDCl3)8.11 (d,J= 7.1Hz, 2H, Ar–H), 7.64 (d,J=7.1Hz, 2H, Ar–H), 5.34 (s, 1H, CH), 4.32 (m, 2H, NCH 2), 3.53 (m, 2H, =NCH 2),2.12 (s, 6H, CH 3), 1.67 (s, 3H, CH 3), –0.45 (s, 3H, AlCH3).
Anal. Calcd for C17H21AlN2O3: C 62.19, H 6.45, N 8.53. Found: C 62.16,H 6.41, N 8.55.
Example 6
The ligand has the structural formula of formula (A), wherein R1Is methyl; r2Is trifluoromethyl, and the reaction process is as follows: 0.34 g of ligand A was dissolved in 10mL of dry cyclohexane under nitrogen atmosphere, and 1.05 times the molar amount of trimethyl ligand A was added at 0 deg.CAnd (3) heating the reaction temperature to 50 ℃ after the reaction temperature naturally rises to room temperature, reacting for 5 hours, vacuumizing the solvent after the reaction is finished, adding dry n-hexane for washing, filtering, collecting, drying and weighing to obtain 0.32 g of solid with the yield of 80.0%.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is methyl; r2The aluminum complex (I) which is trifluoromethyl is successfully synthesized.
1H NMR (400 MHz, CDCl3)8.23 (d,J= 7.1 Hz, 2H, Ar–H), 7.66 (d,J=7.1 Hz, 2H, Ar–H), 5.77 (s, 1H, CH), 4.31 (m, 2H, NCH 2), 3.56 (m, 2H, =NCH 2),2.11 (s, 3H, CH 3), 1.65 (s, 3H, CCH 3), –0.51 (s, 3H, AlCH 3).
Anal. Calcd for C17H18AlF3N2O3: C 53.41, H 4.75, N 7.33. Found: C53.46, H 4.71, N 7.40.
Example 7
The ligand has the structural formula of formula (A), wherein R1Is trifluoromethyl; r2Is phenyl, and the reaction process is as follows: 0.30 g of ligand A is dissolved in 10mL of dry hexane under nitrogen atmosphere, 1.1 times of the molar amount of trimethylaluminum of the ligand A is added at-5 ℃, the reaction temperature naturally rises to room temperature, the mixture is heated to 40 ℃ for reaction for 6 hours, and after the reaction is finished, the mixture is filtered, washed by dry n-hexane, filtered, collected, dried and weighed, so that 0.27 g of solid is obtained, and the yield is 79.4%.
The nuclear magnetic information of the obtained product is shown below, from which it can be seen that R is1Is trifluoromethyl; r2The synthesis of the aluminum complex (I) which is phenyl is successful.
1H NMR (400 MHz, CDCl3)8.23(d,J= 7.2 Hz, 2H, Ar–H), 7.72 (d,J=7.2 Hz, 2H, Ar–H), 7.68-7.52(m, 3H, Ar–H),7.32 (d,J= 7.1 Hz, 2H, Ar–H),6.52 (s, 1H, CH), 4.38 (m, 2H, NCH 2), 3.98 (m, 2H, =NCH 2) 1.68 (s, 1H, CCH 3),–0.52 (s, 3H, AlCH 3).
Anal. Calcd for C22H20AlF3N2O3: C 59.46, H 4.54, N 6.30. Found: C59.49, H 4.56, N 6.36.
Example 8
The ligand has the structural formula of formula (A), wherein R1Is trifluoromethyl; r2Is trifluoromethyl, and the reaction process is as follows: under nitrogen atmosphere, 0.32 g of ligand A is dissolved in 10mL of dry toluene, 1.05 times of the molar weight of trimethylaluminum of the ligand A is added at 0 ℃, after the reaction temperature naturally rises to room temperature, the reaction temperature is heated to 110 ℃ for reaction for 1 hour, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.30 g of solid with the yield of 81.1%.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is trifluoromethyl; r2The aluminum complex (I) which is trifluoromethyl is successfully synthesized.
1H NMR (400 MHz, CDCl3)12.30 (s, 1H, OH), 8.60 (d,J= 7.2 Hz, 2H,Ar–H), 7.72 (d,J= 7.2 Hz, 2H, Ar–H), 6.04 (s, 1H, CH), 4.54 (m, 2H, NCH 2),3.72 (m, 2H, =NCH 2)，2.02 (s, 3H, CH 3)，–0.48 (s, 3H, AlCH 3)。
Anal. Calcd for C17H15AlF6N2O3: C 46.80, H 3.47, N 6.42. Found: C46.84, H 3.53, N 6.38.
Preparation of aluminum Complex (I) from ligand II
Example 9
R1Is methyl, R2Synthesis of ligand ii as methyl: under nitrogen atmosphere, ligand A (R)1Is methyl; r2Is methyl) 0.Dissolving 25 g of the complex in 10mL of dry toluene, adding trimethylaluminum with the molar weight 1.0 time that of the ligand A at the temperature of-10 ℃, heating to 50 ℃ after the reaction temperature naturally rises to room temperature for reaction for 5 hours, adding 50 microliters of water after the reaction is finished, stopping the reaction, separating liquid, collecting an organic phase, drying anhydrous sodium sulfate, and spin-drying the solvent to obtain a crude product, and recrystallizing the crude product by methanol to obtain 0.22 g of a pure product with the yield of 84.6%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)11.02 (s, 1H, OH), 8.10 (d,J= 7.2 Hz, 2H,Ar–H), 7.66 (d,J= 7.2 Hz, 2H, Ar–H), 5.34 (s, 1H, CH), 4.33 (m, 2H, NCH 2),3.56 (m, 2H, =NCH 2), 2.12 (s, 6H, CH 3), 1.67 (s, 3H, CH3).
HRESI-MS: m/z cacld. C16H20N2O3[M-H]-; 287.1394, found: 287.1397.
as can be seen from the above characterization results, the obtained product is R in the above formula (II)1Is methyl; r2A ligand which is a methyl group.
The ligand has the structural formula of formula (II) as above, wherein R1Is methyl; r2The reaction process is as follows: dissolving 0.25 g of ligand II in 10mL of dry toluene in a nitrogen atmosphere, adding trimethylaluminum with the molar weight being 1.1 times that of the ligand II at 0 ℃, heating to 110 ℃ after the reaction temperature naturally rises to room temperature for reaction for 1 hour, vacuumizing the solvent after the reaction is finished, adding dry n-hexane for washing, filtering, collecting, drying and weighing to obtain 0.24 g of solid with the yield of 85.7%. The structural formula of the product is shown as formula I, R1Is methyl; r2Is methyl.
Example 10
R1Is methyl, R2Ligand ii synthesis for trifluoromethyl: under nitrogen atmosphere, ligand A (R)1Is methyl; r2Trifluoromethyl) was dissolved in 10mL of dry cyclohexane, and 1.05 times the molar amount of trimethylaluminum as ligand A was added at 0 ℃ to the reaction mixtureNaturally heating to room temperature, heating to 60 ℃ for reaction for 2 hours, adding 50 microliters of water after the reaction to stop the reaction, separating liquid and collecting an organic phase, drying by using anhydrous sodium sulfate, spin-drying a solvent to obtain a crude product, and recrystallizing the crude product by using methanol to obtain a pure product 0.25 g, wherein the yield is 80.6%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)13.01 (s, 1H，OH), 8.27 (s, 1H, CH=N), 7.64(d, J = 7.4 Hz, 1H, Ar–H), 7.55–7.44 (m, 3H, Ar–H), 6.98–6.88 (m, 1H, Ar–H),6.81–6.72 (m, 1H, Ar–H), 4.38–4.31 (m, 2H, NCH2), 4.18–4.09 (m, 2H, NCH2),2.21 (s, 6H, ArCH3), 1.61 (s, 3H, CH3).
HRESI-MS: m/z cacld. C16H17F3N2O3[M-H]-; 341.1113, found: 341.1117.
as can be seen from the above characterization results, the obtained product is R in the above formula (II)1Is methyl; r2Is a ligand of trifluoromethyl.
The ligand has the structural formula of formula (II) as above, wherein R1Is methyl; r2Is trifluoromethyl, and the reaction process is as follows: under nitrogen atmosphere, 0.30 g of ligand II is dissolved in 10mL of dry cyclohexane, 1.0 time of the molar weight of trimethylaluminum of the ligand II is added at minus 10 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 30 ℃ for reaction for 6 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.30 g of solid with the yield of 88.2%. The structural formula of the product is shown as formula I, R1Is methyl; r2Is trifluoromethyl.
Example 11
R1Is trifluoromethyl, R2Ligand ii synthesis for phenyl: under nitrogen atmosphere, ligand A (R)1Is trifluoromethyl; r2Phenyl) 0.20 g was dissolved in 8 mL of dry hexane, 1.1 times the molar amount of the ligand A trimethylaluminum was added at-5 ℃ and, after the reaction temperature naturally rose to room temperature, the mixture was addedHeating to 40 ℃ for reaction for 6 hours, adding 28 microliters of water after the reaction is finished to stop the reaction, separating liquid and collecting an organic phase, drying the organic phase by using anhydrous sodium sulfate, and spin-drying the solvent to obtain a crude product, and recrystallizing the crude product by using ethanol to obtain a pure product 0.17g, wherein the yield is 81.0%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)12.25 (s, 1H, OH), 8.14 (d,J= 7.2 Hz, 2H,Ar–H), 7.67 (d,J= 7.2 Hz, 2H, Ar–H), 7.61-7.53(m, 3H, Ar–H),7.16 (d,J=6.8 Hz, 2H, Ar–H), 6.45 (s, 1H, CH), 4.37 (m, 2H, NCH 2), 3.97 (m, 2H, =NCH 2),1.66 (s, 3H, CH3).
HRESI-MS: m/z cacld. C21H19F3N2O3[M-H]-; 403.1272, found: 403.1272.
as can be seen from the above characterization results, the obtained product is R in the above formula (II)1Is trifluoromethyl; r2Is a phenyl ligand.
The ligand has the structural formula of formula (II) as above, wherein R1Is trifluoromethyl; r2Is phenyl, and the reaction process is as follows: under nitrogen atmosphere, 0.40 g of ligand II is dissolved in 10mL of dry hexane, 1.2 times of the molar weight of trimethylaluminum of the ligand II is added at-5 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 50 ℃ for reaction for 4 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.36 g of solid with the yield of 81.8 percent. The structural formula of the product is shown as formula I, R1Is trifluoromethyl; r2Is phenyl.
Example 12
R1Is trifluoromethyl, R2Ligand ii synthesis for trifluoromethyl: under nitrogen atmosphere, ligand A (R)1Is trifluoromethyl; r2Trifluoromethyl) is dissolved in 15mL of dry toluene, 1.0 time of the molar weight of the ligand A is added at-5 ℃, the temperature naturally rises to room temperature, the mixture is heated to 100 ℃ for reaction for 1 hour, and the reaction is carried outAfter the reaction is finished, 57 microliters of water is added to stop the reaction, the organic phase is collected by liquid separation, dried by anhydrous sodium sulfate, and the solvent is dried in a spinning mode to obtain a crude product, and the crude product is recrystallized by ethanol to obtain 0.35 g of a pure product, wherein the yield is 83.3%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)12.30 (s, 1H, OH), 8.60 (d,J= 7.2 Hz, 2H,Ar–H), 7.72 (d,J= 7.2 Hz, 2H, Ar–H), 6.04 (s, 1H, CH), 4.54 (m, 2H, NCH 2),3.72 (m, 2H, =NCH 2)，2.02 (s, 3H, CH 3).
HRESI-MS: m/z cacld. C16H13F6N2O3F[M-H]-; 395.0830, found: 395.0818.
as can be seen from the above characterization results, the obtained product is R in the above formula (II)1Is trifluoromethyl; r2Is a ligand of trifluoromethyl.
The ligand has the structural formula of formula (II) as above, wherein R1Is trifluoromethyl; r2Is trifluoromethyl, and the reaction process is as follows: under nitrogen atmosphere, 0.35 g of ligand II is dissolved in 10mL of dry toluene, 1.1 times of the molar weight of trimethylaluminum of the ligand II is added at-5 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 60 ℃ for reaction for 3 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.32 g of solid with the yield of 82.1%. The structural formula of the product is shown as formula I, R1Is trifluoromethyl; r2Is trifluoromethyl.
Preparation of poly-caprolactone
Example 13
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Methyl), 100 μmol benzyl alcohol, 10mL toluene and 10 mmol caprolactone, and then placed at 110oC, in an oil bath, adding a small amount of water to stop the reaction after 4 minutes of reactionPrecipitating with ethanol, washing several times, and vacuum drying at room temperature to obtain 1.10 g product with yield of 96.5% and molecular weight of 2.2 ten thousand.
Example 14
Polycaprolactone was prepared according to the method of example 13 except that: the catalyst used is an aluminum complex of the formula I, R1Is methyl; r2Is trifluoromethyl. After reacting for 2 minutes, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain 1.11g of product, wherein the yield is 97.4%, and the molecular weight is 1.9 ten thousand.
Example 15
Polycaprolactone was prepared according to the method of example 13 except that: the catalyst used is an aluminum complex of the formula I, R1Is trifluoromethyl; r2Is phenyl. After reacting for 3 minutes, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain 1.11g of product, wherein the yield is 97.4%, and the molecular weight is 2.4 ten thousand.
Example 16
Polycaprolactone was prepared according to the method of example 13 except that: the catalyst used is an aluminum complex of the formula I, R1Is trifluoromethyl; r2Is trifluoromethyl. After the reaction is carried out for 1.5 minutes, a small amount of water is added to stop the reaction, ethanol is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at room temperature to obtain 1.12 g of a product, the yield is 98.2 percent, and the molecular weight is 2.0 ten thousand.
Example 17
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Trifluoromethyl), 100 μmol benzyl alcohol, 10mL toluene, and 10 mmol caprolactone, respectively, then 20oC、40oC、60oC、80oC and 100oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein, the reaction is carried out for 30 minutes at 20 ℃ to obtain 1.09 g of product, the yield is 95.6 percent, and the molecular weight is 2.2 ten thousand.
The reaction was carried out at 40 ℃ for 15 minutes to give 1.10 g of product, 96.5% yield, 2.4 ten thousand molecular weight.
The reaction is carried out for 10 minutes at 60 ℃ to obtain 1.11g of product, the yield is 97.4 percent, and the molecular weight is 1.9 ten thousand.
The reaction is carried out for 8 minutes at 80 ℃ to obtain 1.12 g of product, the yield is 98.2 percent, and the molecular weight is 2.1 ten thousand.
The reaction is carried out for 2 minutes at 100 ℃ to obtain 1.12 g of product, the yield is 98.2 percent, and the molecular weight is 2.0 ten thousand.
Example 18
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Methyl), 30 μmol benzyl alcohol, 10mL tetrahydrofuran and 5 mmol-caprolactone, then 30oC, after reacting for 30 minutes, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and drying in vacuum at room temperature to obtain 0.55 g of a product, wherein the yield is 96.5 percent, and the molecular weight is 5.1 ten thousand.
Example 19
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Trifluoromethyl), 30 μmol benzyl alcohol, 10mL toluene, and 10 mmol-caprolactone, and then placed at 50oAnd C, in an oil bath, after reacting for 15 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.11g of a product, wherein the yield is 97.4 percent, and the molecular weight is 7.2 ten thousand.
Example 20
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Is phenyl), 20 mu mol benzyl alcohol, 15mL toluene and 15 mmol-caprolactone, and then the mixture is placed at 90 DEG CoC, oil bath, adding a small amount of water to stop the reaction after 2 minutes of reaction, precipitating with ethanol, washing for several times, and vacuum-drying at room temperatureDrying to obtain 1.65 g of product, the yield is 96.5%, and the molecular weight is 16.1 ten thousand.
Example 21
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Trifluoromethyl), 100 μmol benzyl alcohol, 10mL toluene, and 5 mmol-caprolactone, and then placed at 70oAnd C, in an oil bath, after reacting for 4 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 0.54 g of a product, wherein the yield is 94.7 percent, and the molecular weight is 1.1 ten thousand.
Comparative example 1
Preparation of nickel catalyst: the ligand has the structural formula as shown in formula (II), R1Is trifluoromethyl; r2Is trifluoromethyl, and the reaction process is as follows: dissolving 0.30 g of ligand in 10mL of absolute ethyl alcohol, adding nickel acetate with the molar weight being 1.0 time of that of the ligand at room temperature, heating and refluxing for 12 hours, concentrating the solvent in vacuum after the reaction is finished, adding dichloromethane to precipitate a solid, filtering, washing with hexane, and drying to obtain the nickel catalyst, wherein the structural formula of the nickel catalyst is shown as the following.
Polycaprolactone was prepared according to the method of example 13 except that: the catalyst used was the nickel catalyst described above. After 24 hours of reaction, a small amount of water is added to terminate the reaction, methanol is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at room temperature to obtain 0.38 g, the yield is 33.3 percent, and the molecular weight is 1.3 ten thousand. The nickel catalyst has too low polymerization activity for caprolactone, and is useless.
Comparative example 2
Preparation of aluminum catalyst: the ligand has the formula (LH)2) The reaction process is as follows: dissolving 0.20 g of ligand in 10mL of toluene under the protection of anhydrous oxygen-free inert gas, adding 1.0 time of trimethylaluminum in the molar weight of the ligand at-5 ℃, slowly heating to room temperature, heating to 80 ℃, reacting for 12 hours, concentrating the solvent in vacuum after the reaction is finished, addingAdding dry hexane to separate out solid, filtering, washing with hexane, and drying to obtain the aluminum catalyst, wherein the structural formula of the aluminum catalyst is LAlMe shown in the specification.
Polycaprolactone was prepared according to the method of example 13 except that: the catalyst used was the aluminum catalyst. After 15 minutes of reaction, a small amount of water is added to terminate the reaction, ethanol is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at room temperature to obtain 0.94 g, the yield is 82.5 percent, and the molecular weight is 1.3 ten thousand.
Comparative example 3
Polycaprolactone was prepared according to the method of example 13 except that: the catalyst used was the catalyst used in example 10 of patent 201410609375.8. After 15 minutes of reaction, a small amount of water is added to terminate the reaction, ethanol is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at room temperature to obtain 0.98 g, the yield is 86.0 percent, and the molecular weight is 1.5 ten thousand.
Comparative example 4
The ligand has a structural formula shown in formula (A), wherein R1Is methyl; r2Is trifluoromethyl, and the reaction process is as follows: 0.34 g of ligand A was dissolved in 10mL of dry cyclohexane under a nitrogen atmosphere, triisopropylaluminum in an amount of 1.05 times the molar amount of ligand A was added at 0 ℃ to the solution, the reaction temperature was naturally raised to room temperature, the reaction temperature was heated to 50 ℃ to react for 5 hours, 47. mu.L of water was added to the reaction mixture to stop the reaction, the organic phase was collected by separation, dried over anhydrous sodium sulfate, and the solvent was dried by spinning to obtain a crude product, and it was found that the obtained compound was not changed (isopropyl group did not undergo C = O addition reaction). Triisopropylaluminum failed to undergo addition reaction.
Comparative example 5
Dissolving p-toluenesulfonic acid into xylene, slowly adding 1, 3-propane diamine with equimolar amount of p-toluenesulfonic acid, adding phthalic anhydride with equimolar amount of p-toluenesulfonic acid, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering the solid, washing, and drying to obtain the solid. Dissolving the solid into dichloromethane, slowly dropwise adding an excessive saturated aqueous solution of sodium bicarbonate, reacting at room temperature, separating after the reaction is finished, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain the unilateral phthalic anhydride protected 1, 3-propanediamine. Heating and refluxing unilateral phthalic anhydride protected propane diamine and equimolar hexafluoroacetylacetone in methanol, cooling in a refrigerator after the reaction is finished, separating out a solid, filtering, washing with cold methanol, and drying to obtain a compound LD.
Preparation of aluminum catalyst: under nitrogen atmosphere, 0.30 g of compound LD is dissolved in 10mL of dry toluene, 1.1 time of trimethylaluminum in the molar weight of the compound LD is added at minus 5 ℃, the temperature naturally rises to room temperature, the mixture is heated to 100 ℃ for reaction for 3 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dried n-hexane is added for washing, filtering and drying to obtain 0.27 g of solid with the yield of 79.4 percent, and after the aluminum compound is hydrolyzed, mass spectrometry shows that the ligand can only perform addition reaction on one side to obtain LDAlMe2（HRESI-MS: m/z cacld. C16H12F6N2O3[M-H]-; 393.0676, found: 393.0670）。
Polycaprolactone was prepared according to the method of example 13 except that: the catalyst used was the aluminum catalyst. The mass of the product obtained after the reaction was 0.52 g, the yield was 45.6%, and the molecular weight was 1.2 ten thousand.
Claims (14)
1. A method for catalyzing caprolactone polymerization by using an asymmetric aluminum complex containing an acetylacetone derivative is characterized by comprising the following steps: mixing a catalyst, an organic solvent, a benzyl alcohol cocatalyst and caprolactone, carrying out ring-opening polymerization reaction under the protection of anhydrous, oxygen-free and inert gases, and processing reactants after reaction to obtain polycaprolactone; the catalyst is an asymmetric aluminum complex containing acetylacetone derivatives, and the structural formula of the asymmetric aluminum complex is shown as the following formula I, wherein R1Is trifluoromethyl or methyl, R2Is phenyl, trifluoromethyl or methyl;
2. the method of claim 1, further comprising: r1Is trifluoromethyl, R2Is trifluoromethyl.
3. The method of claim 1, further comprising: the preparation method of the catalyst comprises the following steps: adding the ligand A or the ligand II into an organic solvent at-10 to 0%oAdding trimethylaluminum under C, naturally raising the reaction temperature to room temperature after the addition is finished, and then raising the temperature to 30-110 DEG CoC, reacting, and then, carrying out vacuum drying on the solvent, washing and filtering to obtain the asymmetric aluminum complex containing the acetylacetone derivative shown in the formula I; the structural formulas of the ligand A and the ligand II are shown in the specification, wherein R1Is trifluoromethyl or methyl, R2Is phenyl, trifluoromethyl or methyl;
4. the method of claim 3, wherein: in ligands A and II, R1Is trifluoromethyl, R2Is trifluoromethyl.
5. The method of claim 3, wherein: in the preparation process of the catalyst, the molar ratio of the ligand A or the ligand II to the trimethylaluminum is 1: 1 to 1.3.
6. The method of claim 5, wherein: in the preparation process of the catalyst, the molar ratio of the ligand A or the ligand II to the trimethylaluminum is 1: 1 to 1.05.
7. The method of claim 3, wherein: in the preparation process of the catalyst, the organic solvent is one or two of dry hexane, toluene and cyclohexane; the dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials.
8. The method of claim 3, wherein: in the preparation process of the catalyst, after the temperature is raised to the room temperature, the temperature is raised to 30-110 DEGoC, reacting for 1-12 hours.
9. The method of claim 8, wherein: in the preparation process of the catalyst, after the temperature is raised to the room temperature, the temperature is raised to 40-60 DEGoC, reacting for 3-6 hours.
10. The method of claim 3, wherein: in the preparation process of the catalyst, the reaction is carried out under the protection of inert gas.
11. The method according to any of claims 1-10, characterized by: during ring-opening polymerization, the molar ratio of caprolactone to the catalyst is 50-1500: 1.
12. the method according to any of claims 1-10, characterized by: during ring-opening polymerization reaction, the molar ratio of the benzyl alcohol cocatalyst to the catalyst is 1-3: 1.
13. the method according to any of claims 1-10, characterized by: and during the ring-opening polymerization reaction, the organic solvent is toluene or tetrahydrofuran.
14. The method according to any of claims 1-10, characterized by: during the ring-opening polymerization reaction, the reaction temperature is 20-110 ℃, and the reaction time is 1-60 minutes.
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| CN102260283A (en) * | 2011-04-14 | 2011-11-30 | 华东理工大学 | Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof |
| CN106831843A (en) * | 2017-01-19 | 2017-06-13 | 青岛科技大学 | The preparation method of double (salicylide) the contracting o-phenylenediamine aluminium compounds of asymmetric N, N ' and application |
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| CN102260283A (en) * | 2011-04-14 | 2011-11-30 | 华东理工大学 | Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof |
| CN106831843A (en) * | 2017-01-19 | 2017-06-13 | 青岛科技大学 | The preparation method of double (salicylide) the contracting o-phenylenediamine aluminium compounds of asymmetric N, N ' and application |
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| Title |
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| Aluminium salalen complexes based on 1,2-diaminocyclohexane and their exploitation for the polymerisation of rac-lactide;Stuart L. Hancock等;《Dalton Transactions》;20130315;第42卷;第9279-9285页 * |
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