CN107955147A - Utilize the method for the asymmetric aluminum complex catalysis lactide polymerization of the derivative containing acetylacetone,2,4-pentanedione - Google Patents
Utilize the method for the asymmetric aluminum complex catalysis lactide polymerization of the derivative containing acetylacetone,2,4-pentanedione Download PDFInfo
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- CN107955147A CN107955147A CN201711315043.9A CN201711315043A CN107955147A CN 107955147 A CN107955147 A CN 107955147A CN 201711315043 A CN201711315043 A CN 201711315043A CN 107955147 A CN107955147 A CN 107955147A
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- methyl
- lactide
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 61
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 21
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 11
- 239000003426 co-catalyst Substances 0.000 claims abstract description 5
- 229960004217 benzyl alcohol Drugs 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract 2
- 239000003446 ligand Substances 0.000 claims description 89
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 63
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 52
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 methyl Methyl Chemical group 0.000 claims description 10
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 43
- 238000001035 drying Methods 0.000 description 26
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 230000005311 nuclear magnetism Effects 0.000 description 16
- 238000010438 heat treatment Methods 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
- 230000004044 response Effects 0.000 description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000000926 separation method Methods 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
- 239000003708 ampul Substances 0.000 description 7
- 150000003938 benzyl alcohols Chemical class 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000012869 ethanol precipitation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 150000003613 toluenes Chemical class 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000003808 methanol extraction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000243 solution Substances 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
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 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
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- YVXIQVXKXBYVRO-UHFFFAOYSA-N 2,2,2-trifluoroacetic acid 1,1,1-trifluoropentane-2,4-dione Chemical compound OC(=O)C(F)(F)F.CC(=O)CC(=O)C(F)(F)F YVXIQVXKXBYVRO-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy 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
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical group O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 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
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
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 kind of method of the asymmetric aluminum complex catalysis lactide polymerization using the derivative containing acetylacetone,2,4-pentanedione, comprise the following steps:Catalyst, organic solvent, benzylalcohol auxiliary agent and lactide are mixed, ring-opening polymerization is carried out under anhydrous and oxygen-free and inert gas shielding, carries out reactant after reaction to handle to obtain polylactide;The catalyst is the asymmetric aluminum complex of the derivative containing acetylacetone,2,4-pentanedione.For the present invention using the asymmetric aluminum complex of the derivative containing acetylacetone,2,4-pentanedione as catalyst, benzylalcohol is co-catalyst, and reaction controllability is good, the stereoselectivity of catalyst is high, obtained polylactide molecular weight is controllable, yield is high, has excellent physicochemical property, disclosure satisfy that the needs in market.
Description
Technical field
The present invention relates to a kind of method of lactide polymerization, and in particular to a kind of to utilize the non-right of the derivative containing acetylacetone,2,4-pentanedione
Claim the method for aluminum complex catalysis lactide polymerization.
Background technology
Conventional plastic using oil as raw material has unrivaled advantage, but have two it is fatal the shortcomings that:It is non-renewable
And non-biodegradable.In the case where oil faces exhaustion as non-renewable resources, the high molecular material of petroleum is relied on
Fast development be subject to severely restricts, and macromolecule polymeric material is difficult to degrade, substantial amounts of macromolecule polymeric material discarded object
Long-term accumulate in pollutes also gradually exacerbation caused by environment for human survival in actual life.Therefore find instead of oil can be again
Production-goods source is very urgent.
Because polyester is nontoxic, nonirritant, and has good biocompatibility, therefore polyester is biodegradable
The high molecular material of environmental type, the substitute using polyester material as oil product have been to be concerned by more and more people.
In natural living environment, discarded polylactone material can thoroughly resolve into water and carbon dioxide, ring by the microorganism in soil
Protect and renewable.Polyester is widely used in medicine and field of environment protection, such as operation suture thread, packaging, drug controlled release
With tissue engineering bracket etc..The performance that the excellent biocompatibility of polylactone, biological degradability and sustainable development utilize, makes
It has become 21 century most promising high molecular material.
The advantages of method of synthesizing polyester easily is the ring-opening polymerisation method of cyclic lactone, this synthetic method be:Polymerization
Controllability, relatively narrow molecular weight distribution.Currently used catalyst is the complex that ligand and metal are formed mostly, is matched somebody with somebody in metal
In mixture catalyst, the selection of the selecting catalyst of ligand and metal is for the speed of ring-opening polymerization, the property of products obtained therefrom
Can be all very crucial, in the case of same metal, often ligand replacement and selection can show it is unexpected catalysis effect
Fruit, in the case of same ligand, the replacement of metal can also produce different catalytic effects, therefore study that new, performance is good
Catalyst is very necessary.
The content of the invention
The present invention provides a kind of asymmetric aluminum complex catalysis lactide polymerization using the derivative containing acetylacetone,2,4-pentanedione
Method, this method is easy to operate, using the asymmetric aluminum complex of the derivative containing acetylacetone,2,4-pentanedione voluntarily researched and developed as catalyst, reaction
Controllability is good, and the stereoselectivity of catalyst is high, and obtained polylactide molecular weight is controllable, yield is high.
Technical solution of the present invention is as follows:
The present invention provides a kind of asymmetric aluminum complex catalyst of the special derivative containing acetylacetone,2,4-pentanedione of structure, the catalyst
Structural formula such as following formula(Ⅰ)It is shown:
。
The asymmetric aluminum complex of the derivative of the invention containing acetylacetone,2,4-pentanedione passes through the selection to ligand structure and and metallic aluminium
Coordination there is excellent performance, in ligand the selection of substituent urged for the aluminum complex as cyclic lactone ring-opening polymerization
The catalytic performance of agent has considerable influence.Wherein, R1For trifluoromethyl or methyl, R2To be catalyzed when phenyl, trifluoromethyl or methyl
Excellent performance, R1、R2It may be the same or different.Further, consider from steric hindrance, cloud density etc., greatly
Steric group(Phenyl)It can make the stereoselectivity of aluminum complex increase, work as R1For trifluoromethyl, R2For phenyl when three-dimensional selection
Property higher.
The above-mentioned asymmetric aluminum complex catalyst for containing acetylacetone,2,4-pentanedione derivative of the present invention is by ligand and trimethyl aluminium
Reaction obtains, and its preparation method comprises the following steps:Ligand A is added in organic solvent, then -10~0oThree are added under C
Aluminium methyl, after reaction temperature is warmed to room temperature naturally, heating reacted, reaction mixture by vacuum drain solvent, washing,
Filtering, obtains the asymmetric aluminum complex of the derivative containing acetylacetone,2,4-pentanedione.
Ligand A and the equation that trimethyl aluminium reacts are as follows, and the structural formula of wherein ligand A is shown below, R1For trifluoro
Methyl or methyl, are preferably trifluoromethyl;R2It is preferably phenyl for phenyl, trifluoromethyl or methyl:
In above-mentioned preparation method, the preparation method of ligand A comprises the following steps:P-methyl benzenesulfonic acid is dissolved into dimethylbenzene, first
The ethylenediamine of p-methyl benzenesulfonic acid equimolar amounts is slowly added into, adds the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, so
Heating carries out back flow reaction afterwards, is cooled to room temperature after reaction, filters to take solid, obtained solid is dissolved into dichloromethane
In, excessive saturated sodium bicarbonate aqueous solution is then slowly added dropwise and sloughs p-methyl benzenesulfonic acid, liquid separation after reaction is organic by gained
Mutually dried with anhydrous magnesium sulfate, be then spin-dried for solvent, obtain the ethylenediamine of unilateral phthalic anhydride protection;By unilateral O-phthalic
In methyl alcohol, heating carries out back flow reaction, reaction for the acetylacetone,2,4-pentanedione derivative dissolving of the ethylenediamine and equimolar amounts of acid anhydrides protection
Terminate postcooling, filtering, obtained solid is washed with cold methanol, is dry, obtains ligand A;The structural formula of the acetylacetone,2,4-pentanedione derivative
As shown in following formula B, wherein R1For trifluoromethyl or methyl, preferably trifluoromethyl, R2For phenyl, trifluoromethyl or methyl, preferably
For phenyl.
In above-mentioned preparation method, addition reaction occurs for ligand A and trimethyl aluminium, and the methyl of trimethyl aluminium adds to ligand A
In C=O double bonds on, C=O double bonds become C-O singly-bounds.Found by nuclear-magnetism characterizationδThere is one group of CH in the range of=1.5-2.03
Characteristic peak, this characteristic peak is exactly NC (O) (Ar) CH 3Middle CH3Characteristic peak.
In above-mentioned preparation method, the molar ratio 1 of ligand A and trimethyl aluminium:1~1.3, preferably 1:1~1.05.
In above-mentioned preparation method, the organic solvent is one or both of dry hexane, toluene and hexamethylene, excellent
Elect dry hexane or toluene as.
In above-mentioned preparation method, consumption of organic solvent is reaction raw materials(Ligand A and trimethyl aluminium)The 5~40 of gross mass
Times.
In above-mentioned preparation method, react and carried out under gas shield, the gas is inert gas or nitrogen.
In above-mentioned preparation method, reaction nature rises to 30~110 again after being raised to room temperatureoC is reacted, such as 30oC、
40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC, preferably 40~60oC.30~110oC(It is preferred that 40~60oC)
When the time reacted is 1~12 small, when being preferably 3~6 small.After reaction, precipitation is washed with n-hexane.
The asymmetric aluminum complex of the derivative of the present invention containing acetylacetone,2,4-pentanedione is the compound described in formula II
Intermediate product, the asymmetric aluminum complex of the derivative containing acetylacetone,2,4-pentanedione is more sensitive to water, after ligand A and trimethyl aluminium reaction
Reaction solution in add water and be sufficiently stirred and can hydrolyze aluminum complex, through liquid separation, collect organic phase, at organic phase recycling design
Reason, compound of the gained residue described in through recrystallization as formula II.Therefore, preparing aluminum complex will be in anhydrous and proton solvent
In the case of carry out.In addition, using the compound described in formula II as raw material, ligand A is replaced with into the compound described in formula II, according to
The preparation method of the asymmetric aluminum complex of the above-mentioned derivative containing acetylacetone,2,4-pentanedione can also obtain I derivative containing acetylacetone,2,4-pentanedione of formula again
Asymmetric aluminum complex.
When preparing the asymmetric aluminum complex of the derivative containing acetylacetone,2,4-pentanedione with the compound described in formula II, organic solvent is dry
One or both of dry hexane, toluene and hexamethylene, are preferably hexane or toluene.Consumption of organic solvent is reaction raw materials
(Compound and trimethyl aluminium described in formula II)5~40 times of gross mass.Reaction is recrystallized after terminating with dry hexane,
Obtain the asymmetric aluminum complex of high I derivative containing acetylacetone,2,4-pentanedione of formula of purity.
The asymmetric aluminum complex of the derivative of the invention containing acetylacetone,2,4-pentanedione is complex, and N, N, O, O and aluminium of ligand are carried out
Coordination, the structure of complex and classical cyclic lactone catalyst(salenAl)Structure it is very similar, excellent catalytic effect, has
Higher stereoselectivity, is a kind of catalyst of cyclic lactone ring-opening polymerization well.
Catalyst of the asymmetric aluminum complex of the derivative of the invention containing acetylacetone,2,4-pentanedione as cyclic lactone ring-opening polymerization
When, the ring-opening polymerisation of lactide can be catalyzed, obtains a series of polylactide, lactide can be levorotatory lactide again, interior
Meso-lactide, rac-lactide.The asymmetric aluminum complex of the derivative of the invention containing acetylacetone,2,4-pentanedione is carried out as catalyst
During cyclic lactone ring-opening polymerization, the polymer molecule Mass Distribution reacted is narrow, molecular weight is controllable, yield is high, particularly
When rac-lactide polymerization is catalyzed, the high isotaxy polylactide of fusing point is obtained, shows higher three-dimensional choosing
Selecting property, stereoselectivity reach as high asP m = 0.84。
The asymmetric aluminum complex of the derivative of the invention containing acetylacetone,2,4-pentanedione is used as the catalyst of cyclic lactone ring-opening polymerization
When, work as R1For trifluoromethyl, R2For phenyl when stereoselectivity highest.
The present invention specifically provides a kind of asymmetric aluminum complex using the derivative containing acetylacetone,2,4-pentanedione and is catalyzed lactide
The method of polymerization, comprises the following steps:By asymmetric aluminum complex catalyst, organic solvent, the benzyl of the derivative containing acetylacetone,2,4-pentanedione
Alcohol co-catalyst and lactide mixing, carry out ring-opening polymerization under anhydrous and oxygen-free and inert gas shielding, will be anti-after reaction
Thing is answered to carry out handling to obtain polylactide.The lactide can be levorotatory lactide, Study of Meso-Lactide, rac-lactide.
In above-mentioned ring-opening polymerization, lactide rubs with the asymmetric aluminum complex catalyst of the derivative containing acetylacetone,2,4-pentanedione
You are than being 50~1500:1, such as 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 above-mentioned ring-opening polymerization, organic solvent used in reaction is toluene or tetrahydrofuran, preferably toluene.
In above-mentioned ring-opening polymerization, benzylalcohol co-catalyst and the asymmetric aluminum complex of the derivative containing acetylacetone,2,4-pentanedione are catalyzed
The molar ratio of agent is 1~3:1.
In above-mentioned ring-opening polymerization, polymeric reaction temperature be 20~110 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
℃、70℃、80℃、90℃、100℃、110℃.With the rise of polymeric reaction temperature, the stereoselectivity of catalyst has reduction
Trend, catalytic activity has elevated trend, when reaction temperature is at 80 DEG C, solid when being catalyzed to rac-lactide
Selectivity is reachableP m=0.66, when reaction temperature is at 20 DEG C, stereoselectivity when being catalyzed to rac-lactide can
ReachP m = 0.84。
In above-mentioned ring-opening polymerization, polymerization reaction time be 1-1440 minutes, such as 1 minute, 10 minutes, 30 minutes,
40 minutes, 60 minutes, 120 minutes, 240 minutes, 600 minutes, 900 minutes, 1200 minutes, 1440 minutes etc..
In above-mentioned ring-opening polymerization, cold methanol or ethanol purification polylactone are added after reaction, obtains polylactone after purification.
The molecular weight controllability of gained polylactide is high, can be adjusted in the range of 1-17 ten thousand.
The asymmetric aluminum complex catalyst of the derivative of the invention containing acetylacetone,2,4-pentanedione is reacted by ligand and trimethyl aluminium and obtained,
Preparation method is simple, and cost is low, and product yield is high, and catalyst structure changes divalence N, the N of various, metal center aluminium and ligand,
O, O are coordinated, and catalytic activity is high, stereoselectivity is good, reaction rate is fast, is a kind of very good catalyst.The present invention contains second
During the asymmetric aluminum complex catalysis propiolactone ring-opening polymerization of acyl acetone derivatives, the polymer reacted is benzyloxy
The polymer of end-blocking, molecular vibrational temperature is narrow, molecular weight is controllable, yield is high, particularly when being catalyzed rac-lactide polymerization
The high isotaxy polylactide of fusing point can be obtained, shows higher stereoselectivity, stereoselectivity reaches as high as
0.84。
Embodiment
The present invention is further illustrated below by specific embodiment, but the present invention is not limited thereto, and specific protection domain is shown in
Claim.
In following embodiments, the stereoselectivity of isotaxy polylactide is carried out using nuclear magnetic resonance same core decoupling hydrogen spectrum
Test.
Prepare the ethylenediamine (a) of unilateral protection
0.50 g p-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into the ethylenediamine of p-methyl benzenesulfonic acid equimolar amounts, then
The phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, heating reflux reaction 8h are added, reaction is cooled to room temperature after terminating will
Solid filters, and washing, is dried to obtain solid.Solid is dissolved into dichloromethane, the full of excessive sodium acid carbonate is slowly added dropwise
P-methyl benzenesulfonic acid is sloughed with aqueous solution, is reacted at room temperature, liquid separation after reaction, is dried with anhydrous magnesium sulfate, be spin-dried for solvent, obtained
0.48 g of ethylenediamine of unilateral phthalic anhydride protection, yield 87.3%.Reaction equation is as follows:
Prepare the unsymmetric ligand of the derivative containing acetylacetone,2,4-pentanedione(A)
The unsymmetric ligand A of the derivative containing acetylacetone,2,4-pentanedione is passed through by the ethylenediamine of unilateral protection and acetylacetone,2,4-pentanedione or derivatives thereof
What condensation reaction obtained, illustrate below to synthesizing different ligand A.
Embodiment 1
Synthesized ligand structure formula such as above formula(A), wherein R1For methyl;R2For methyl, reaction process is:By the second of unilateral protection
Diamines(a)The acetylacetone,2,4-pentanedione of 0.30 g and equimolar amounts is added in 12 mL methanol, and when heating reflux reaction 12 is small, reaction terminates
Later cold filtration is simultaneously washed with cold methanol, is filtered, and collects and drying is weighed, obtain 0.35 g solids, yield 81.4%.
Products therefrom nuclear-magnetism information is as follows, and R is can be seen that from nuclear-magnetism information1For methyl;R2For methyl ligand synthesis into
Work(.
1H NMR (400 MHz, CDCl3) δ 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.
Embodiment 2
Synthesized ligand structure formula such as above formula(A), wherein R1For methyl;R2For trifluoromethyl, reaction process is:By unilateral protection
Ethylenediamine(a)The trifluoroacetylacetone (TFA) of 0.20 g and equimolar amounts is added in 10 mL methanol, when heating reflux reaction 12 is small,
Reaction terminates later cold filtration and is washed with cold methanol, filters, and collects and drying is weighed, obtain 0.30 g solids, yield
88.2%。
Products therefrom nuclear-magnetism information is as follows, and R is can be seen that from nuclear-magnetism information1For methyl;R2Closed for the ligand of trifluoromethyl
Into success.
1H NMR (400 MHz, CDCl3) δ 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. C15H12F3N2O3 F[M-
H]-; 325.0802, found: 325.0804.
Embodiment 3
Synthesized ligand structure formula such as above formula(A), wherein R1For trifluoromethyl;R2For phenyl, reaction process is:By unilateral protection
Ethylenediamine(a)The benzoyltrifluoroacetone of 0.25 g and equimolar amounts is added in 20 mL methanol, and heating reflux reaction 12 is small
When, reaction terminates later cold filtration and is washed with cold methanol, filters, and collects and drying is weighed, obtain 0.45 g solids, yield
88.2%。
Products therefrom nuclear-magnetism information is as follows, and R is can be seen that from nuclear-magnetism information1For trifluoromethyl;R2Closed for the ligand of phenyl
Into success.
1H NMR (400 MHz, CDCl3) δ 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.
Embodiment 4
Synthesized ligand structure formula such as above formula(A), wherein R1For trifluoromethyl;R2For trifluoromethyl, reaction process is:Will be unilateral
The ethylenediamine of protection(a)The hexafluoroacetylacetone of 0.40 g and equimolar amounts is added in 20 mL methanol, and heating reflux reaction 10 is small
When, reaction terminates later cold filtration and is washed with cold methanol, filters, and collects and drying is weighed, obtain 0.66 g solids, yield
82.5%。
Products therefrom nuclear-magnetism information is as follows, and R is can be seen that from nuclear-magnetism information1For trifluoromethyl;R2For matching somebody with somebody for trifluoromethyl
Body synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 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. C15H9F6N2O3 F[M-H]-; 379.0518, found:
379.0520.
Aluminum complex is prepared using ligand A as raw material(I)
The aluminum complex of the derivative containing acetylacetone,2,4-pentanedione is by ligand A and trimethyl aluminium is eliminated by alkyl and alkyl addition reaction shape
Into complex, reaction equation is as follows.
Embodiment 5
Ligand structure formula such as above formula used(A), wherein R1For methyl;R2For methyl, reaction process is:In a nitrogen atmosphere, will
0.30 g of ligand A are dissolved in 10 mL dry toluenes, and the trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, are treated anti-
After answering temperature to be raised to room temperature naturally, be heated to 90 DEG C reaction 2 it is small when, reaction terminate after vacuum drain solvent, add dry
N-hexane washs, filtering, collects and drying is weighed, obtain 0.31 g solids, yield 86.1%.
Products therefrom nuclear-magnetism information is as follows, and R is can be seen that from nuclear-magnetism information1For methyl;R2For the aluminum complex of methyl(I)
Synthesize successfully.
1H NMR (400 MHz, CDCl3) δ8.11 (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.
Embodiment 6
Ligand structure formula such as above formula used(A), wherein R1For methyl;R2For trifluoromethyl, reaction process is:Under nitrogen atmosphere,
0.34 g of ligand A are dissolved in 10 mL drying hexamethylenes, the trimethyl aluminium of ligand 1.05 times of moles of A is added at 0 DEG C,
After question response temperature is raised to room temperature naturally, heating reaction temperature to 50 DEG C reaction 5 it is small when, reaction terminate after vacuum drain it is molten
Agent, adds dry n-hexane washing, filtering, is collected and drying is weighed, and obtains 0.32 g solids, yield 80.0%.
Products therefrom nuclear-magnetism information is as follows, and R is can be seen that from nuclear-magnetism information1For methyl;R2Coordinate for the aluminium of trifluoromethyl
Thing(I)Synthesize successfully.
1H NMR (400 MHz, CDCl3) δ8.23 (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: C 53.46, H
4.71, N 7.40.
Embodiment 7
Ligand structure formula such as above formula used(A), wherein R1For trifluoromethyl;R2For phenyl, reaction process is:Under nitrogen atmosphere,
0.30 g of ligand A are dissolved in 10 mL drying hexanes, the trimethyl aluminium of ligand 1.1 times of moles of A is added at -5 DEG C, is treated
After reaction temperature is raised to room temperature naturally, be heated to 40 DEG C reaction 6 it is small when, reaction terminate later filtering and with drying n-hexane
Washing, filtering, is collected and drying is weighed, and obtains 0.27 g solids, yield 79.4%.
The nuclear-magnetism information of products obtained therefrom is as follows, it can be seen that R1For trifluoromethyl;R2For the aluminum complex of phenyl
(I)Synthesize successfully.
1H NMR (400 MHz, CDCl3) δ8.23(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: C 59.49, H
4.56, N 6.36.
Embodiment 8
Ligand structure formula such as above formula used(A), wherein R1For trifluoromethyl;R2For trifluoromethyl, reaction process is:In blanket of nitrogen
Under, 0.32 g of ligand A are dissolved in 10 mL dry toluenes, the trimethyl aluminium of ligand 1.05 times of moles of A is added at 0 DEG C,
After question response temperature is raised to room temperature naturally, heating reaction temperature to 110 DEG C reaction 1 it is small when, reaction terminate after vacuum drain it is molten
Agent, adds dry n-hexane washing, filtering, is collected and drying is weighed, and obtains 0.30 g solids, yield 81.1%.
Products therefrom nuclear-magnetism information is as follows, and R is can be seen that from nuclear-magnetism information1For trifluoromethyl;R2For the aluminium of trifluoromethyl
Complex(I)Synthesize successfully.
1H NMR (400 MHz, CDCl3) δ 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: C
46.84, H 3.53, N 6.38.
Aluminum complex is prepared for raw material with ligand II(I)
Embodiment 9
R1For methyl, R2Synthesized for the ligand II of methyl:In a nitrogen atmosphere, by ligand A(R1For methyl;R2For methyl)0.25
G is dissolved in 10 mL dry toluenes, and the trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, and question response temperature is natural
After being raised to room temperature, be heated to 50 DEG C of reactions 5 it is small when, after reaction terminates, add 50 microlitres of water and stop reaction, liquid separation is collected organic
Phase, anhydrous sodium sulfate drying, is spin-dried for solvent, obtains crude product, by crude product through recrystallizing methanol, obtain 0.22 g of net product, yield
84.6 %。
Products obtained therefrom is characterized, it is as a result as follows:
1H NMR (400 MHz, CDCl3) δ 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.
Can be seen that products obtained therefrom from above characterization result is above formula(Ⅱ)Middle R1For methyl;R2For the ligand of methyl.
Ligand structure formula such as above formula used(II), wherein R1For methyl;R2For methyl, reaction process is:In nitrogen atmosphere
Under, 0.25 g of ligand i I are dissolved in 10 mL dry toluenes, the trimethyl of ligand i 1.1 times of moles of I is added at 0 DEG C
Aluminium, after question response temperature is raised to room temperature naturally, be heated to 110 DEG C reaction 1 it is small when, reaction terminate after vacuum drain solvent, add
Enter dry n-hexane washing, filtering, is collected and drying is weighed, and obtains 0.24 g solids, yield 85.7%.Product structure formula such as formula I
It is shown, R1For methyl;R2For methyl.
Embodiment 10
R1For methyl, R2Synthesized for the ligand II of trifluoromethyl:Under nitrogen atmosphere, by ligand A(R1For methyl;R2For fluoroform
Base)0.30 g is dissolved in 10 mL drying hexamethylenes, and the trimethyl aluminium of ligand 1.05 times of moles of A, question response are added at 0 DEG C
After temperature is raised to room temperature naturally, heating reaction temperature to 60 DEG C of reactions 2 it is small when, 50 microlitres of water are added after reaction and stop reaction, point
Liquid collects organic phase, and anhydrous sodium sulfate drying, is spin-dried for solvent, obtains crude product, by crude product through recrystallizing methanol, obtain net product
0.25 g, yield 80.6%.
Products obtained therefrom is characterized, it is as a result as follows:
1H NMR (400 MHz, CDCl3) δ13.01 (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.
Can be seen that products obtained therefrom from above characterization result is above formula(Ⅱ)Middle R1For methyl;R2For the ligand of trifluoromethyl.
Ligand structure formula such as above formula used(II), wherein R1For methyl;R2For trifluoromethyl, reaction process is:In blanket of nitrogen
Under, 0.30 g of ligand i I are dissolved in 10 mL drying hexamethylenes, the front three of ligand i 1.0 times of moles of I is added at -10 DEG C
Base aluminium, after question response temperature is raised to room temperature naturally, be heated to 30 DEG C reaction 6 it is small when, reaction terminate after vacuum drain solvent,
Dry n-hexane washing is added, filtering, is collected and drying is weighed, and obtains 0.30 g solids, yield 88.2%.Product structure formula
As shown in formula I, R1For methyl;R2For trifluoromethyl.
Embodiment 11
R1For trifluoromethyl, R2Synthesized for the ligand II of phenyl:Under nitrogen atmosphere, by ligand A(R1For trifluoromethyl;R2For benzene
Base)0.20 g is dissolved in 8 mL drying hexanes, and the trimethyl aluminium of ligand 1.1 times of moles of A, question response temperature are added at -5 DEG C
After degree nature is raised to room temperature, be heated to 40 DEG C of reactions 6 it is small when, reaction adds 28 microlitres of water and stops reaction, liquid separation receipts after terminating
Collect organic phase, anhydrous sodium sulfate drying, is spin-dried for solvent, obtains crude product, by crude product through ethyl alcohol recrystallization, obtain net product 0.17
G, yield 81.0%.
Products obtained therefrom is characterized, it is as a result as follows:
1H NMR (400 MHz, CDCl3) δ 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.
Can be seen that products obtained therefrom from above characterization result is above formula(Ⅱ)Middle R1For trifluoromethyl;R2For the ligand of phenyl.
Ligand structure formula such as above formula used(II), wherein R1For trifluoromethyl;R2For phenyl, reaction process is:In blanket of nitrogen
Under, 0.40 g of ligand i I are dissolved in 10 mL drying hexanes, the trimethyl of ligand i 1.2 times of moles of I is added at -5 DEG C
Aluminium, after question response temperature is raised to room temperature naturally, be heated to 50 DEG C reaction 4 it is small when, reaction terminate after vacuum drain solvent, add
Enter dry n-hexane washing, filtering, is collected and drying is weighed, and obtains 0.36 g solids, yield 81.8%.Product structure formula is such as
Shown in formula I, R1For trifluoromethyl;R2For phenyl.
Embodiment 12
R1For trifluoromethyl, R2Synthesized for the ligand II of trifluoromethyl:Under nitrogen atmosphere, by ligand A(R1For trifluoromethyl;R2For
Trifluoromethyl)0.40 g is dissolved in 15 mL dry toluenes, and the trimethyl aluminium of ligand 1.0 times of moles of A is added at -5 DEG C, is treated
After reaction temperature is raised to room temperature naturally, be heated to 100 DEG C of reactions 1 it is small when, reaction adds 57 microlitres of water after terminating and stops instead
Should, organic phase is collected in liquid separation, and anhydrous sodium sulfate drying, is spin-dried for solvent, obtains crude product, by crude product through ethyl alcohol recrystallization, obtain pure
0.35 g of product, yield 83.3%.
Products obtained therefrom is characterized, it is as a result as follows:
1H NMR (400 MHz, CDCl3) δ 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. C16H13F6N2O3 F[M-H]-; 395.0830, found: 395.0818.
Can be seen that products obtained therefrom from above characterization result is above formula(Ⅱ)Middle R1For trifluoromethyl;R2For trifluoromethyl
Ligand.
Ligand structure formula such as above formula used(II), wherein R1For trifluoromethyl;R2For trifluoromethyl, reaction process is:In nitrogen
Under atmosphere, 0.35 g of ligand i I are dissolved in 10 mL dry toluenes, the three of ligand i 1.1 times of moles of I is added at -5 DEG C
Aluminium methyl, after question response temperature is raised to room temperature naturally, be heated to 60 DEG C reaction 3 it is small when, reaction terminate after vacuum drain it is molten
Agent, adds dry n-hexane washing, filtering, is collected and drying is weighed, and obtains 0.32 g solids, yield 82.1%.Product structure
Formula is as shown in formula I, R1For trifluoromethyl;R2For trifluoromethyl.
Prepare polylactide
Embodiment 13
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 100 μm of ol catalyst(Aluminum complex shown in formula I, R1For methyl;R2For methyl), 100 μm of ol benzylalcohols, 20 mL toluene
And 10 mmol rac-lactide, then 20oAdd a small amount of water after when C reactions 22 are small and terminate reaction, with ethanol precipitation,
Washing for several times, is dried in vacuo, obtains 1.36 grams of products, yield 94.4% at room temperature.Products therefrom is isotaxy polylactide, point
Son amount 2.6 ten thousand, isotaxy stereoselectivityP m= 0.78。
Embodiment 14
Method according to embodiment 13 prepares polylactide, unlike:Catalyst used is aluminum complex, R shown in formula I1
For methyl;R2For trifluoromethyl.React 20 it is small when after add a small amount of water and terminate reaction, with ethanol precipitation, washing for several times, room temperature
Lower vacuum drying, obtains 1.35 g products, yield 93.8%, and molecular weight is 2.7 ten thousand, isotaxy stereoselectivityP m= 0.81。
Embodiment 15
Method according to embodiment 13 prepares polylactide, unlike:Catalyst used is aluminum complex, R shown in formula I1
For trifluoromethyl;R2For phenyl.React 24 it is small when after add a small amount of water and terminate reaction, with ethanol precipitation, washing for several times, room temperature
Lower vacuum drying, obtains 1.37 g products, yield 95.1%, and molecular weight is 2.8 ten thousand, isotaxy stereoselectivityP m= 0.84。
Embodiment 16
Method according to embodiment 13 prepares polylactide, unlike:Catalyst used is aluminum complex, R shown in formula I1
For trifluoromethyl;R2For trifluoromethyl.React 19 it is small when after add a small amount of water and terminate reaction, with ethanol precipitation, washing for several times,
It is dried in vacuo at room temperature, obtains 1.42 g products, yield 98.6%, molecular weight is 2.6 ten thousand, isotaxy stereoselectivityP m=
0.82。
Embodiment 17
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 100 μm of ol catalyst(Aluminum complex shown in formula I, R1For trifluoromethyl;R2For phenyl), 100 μm of ol benzylalcohols, 10 mL
The rac-lactide of toluene and 10 mmol, then respectively 40oC、60oC and 80oReact, add after reaction few under C
Measure water and terminate reaction, with methanol extraction, washing for several times, be dried in vacuo at room temperature.
Wherein, 1.38 grams of products are obtained when 40 DEG C of reactions 20 are small, yield 95.8%, molecular weight 2.6 ten thousand,P m = 0.79。
When 60 DEG C of reactions 15 are small, 1.39 grams of products are obtained, yield 96.5%, molecular weight 2.4 ten thousand,P m = 0.72。
When 80 DEG C of reactions 13 are small, 1.42 grams of products are obtained, yield 98.6%, molecular weight 2.5 ten thousand,P m = 0.66。
Embodiment 18
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 200 μm of ol catalyst(Aluminum complex shown in formula I, R1For methyl;R2For methyl), 200 μm of ol benzylalcohols, 20 mL tetrahydrochysenes
The levorotatory lactide of furans and 10 mmol, then 30oA small amount of water is added after when C reactions 20 are small and terminates reaction, is sunk with ethanol
Form sediment, wash for several times, be dried in vacuo at room temperature, obtain 1.38 grams of products, yield 95.8%, molecular weight 1.0 ten thousand.
Embodiment 19
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 10 μm of ol catalyst(Aluminum complex shown in formula I, R1For methyl;R2For trifluoromethyl), 10 μm of ol benzylalcohols, 10 mL tetra-
The Study of Meso-Lactide of hydrogen furans and 5 mmol, is subsequently placed in 50oIn the oil bath of C, when reaction 13 is small after to add a small amount of water whole
Only react, with ethanol precipitation, washing for several times, be dried in vacuo at room temperature, obtain 0.68 gram of product, yield 94.4%, molecular weight 10.8
Ten thousand.
Embodiment 20
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 10 μm of ol catalyst(Aluminum complex shown in formula I, R1For trifluoromethyl;R2For trifluoromethyl), 30 μm of ol benzylalcohols, 20
The levorotatory lactide of mL toluene and 10 mmol, is subsequently placed in 90oIn the oil bath of C, when reaction 3 is small after add a small amount of water and terminate
Reaction, with ethanol precipitation, washing for several times, is dried in vacuo, obtains 1.37 grams of products, yield 95.1%, molecular weight 7.4 ten thousand at room temperature.
Embodiment 21
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 10 μm of ol catalyst(Aluminum complex shown in formula I, R1For trifluoromethyl;R2For trifluoromethyl)), 20 μm of ol benzylalcohols, 20
The levorotatory lactide of mL toluene and 15 mmol, is subsequently placed in 110oIn the oil bath of C, when reaction 3 is small after add a small amount of water and terminate
Reaction, with ethanol precipitation, washing for several times, is dried in vacuo, obtains 2.10 grams of products, yield 97.2%, molecular weight 16.9 ten thousand at room temperature.
Comparative example 1
The preparation of Raney nickel:Ligand structure formula such as above formula used(II), R1For trifluoromethyl;R2For trifluoromethyl, reacted
Cheng Wei:0.30 g of ligand is dissolved in 10 mL absolute ethyl alcohols, the nickel acetate of 1.0 times of ligand moles is added at room temperature, heats back
When stream reaction 12 is small, reaction is concentrated in vacuo solvent after terminating, and adds dichloromethane and separates out solid, filters and washed with hexane,
It is dry that Raney nickel, its structural formula are as follows.
Method according to embodiment 21 prepares polylactide, unlike:Catalyst used is above-mentioned Raney nickel.Instead
Answer 24 it is small when after add a small amount of water and terminate reaction, with methanol extraction, washing for several times, be dried in vacuo at room temperature, obtain 0.46 gram of product,
21.3 % of yield, molecular weight 3.1 ten thousand.The Raney nickel is too low to the polymerization activity of lactide, is not worth.
Comparative example 2
The preparation of Al catalysts:Ligand structure formula such as following formula used(LH2), reaction process is:In anhydrous and oxygen-free and inert gas
Under protection, 0.20 g of ligand is dissolved in 10 mL toluene, the trimethyl aluminium of 1.0 times of ligand moles is added at -5 DEG C, is delayed
It is slow be warmed to room temperature after be heated to 80 DEG C of reactions 12 it is small when, reaction is concentrated in vacuo solvent after terminating, and adds dry hexane and separates out admittedly
Body, filters and is simultaneously washed with hexane, dry Al catalysts, its structural formula LAlMe as follows.
Method according to embodiment 17 prepares polylactide, unlike:Catalyst used is the Al catalysts.In nothing
Reacted under water anaerobic and inert gas shielding, sequentially add 100 in the ampulla after being toasted with high pure nitrogen gas washing first
μm ol catalyst, 100 μm of ol benzylalcohols, the rac-lactide of 10 mL toluene and 10 mmol, then respectively 20oC and
80oReacted under C, add a small amount of water after reaction and terminate reaction, with methanol extraction, washing for several times, be dried in vacuo at room temperature.
Wherein, generated when 20 DEG C of reactions 36 are small without product, illustrate that the catalyst can not be catalyzed third at a lower temperature
The polymerization of lactide.
1.15 grams of products, 79.9 % of yield, molecular weight 1.4 ten thousand, the three-dimensional selection of isotaxy are obtained when 80 DEG C of reactions 24 are small
PropertyP m = 0.53.Compare with the Al catalysts of embodiment 17, stereoselectivity and activity are all than relatively low.
Comparative example 3
Method according to embodiment 13 prepares polylactide, unlike:Catalyst used is patent 201410609375.8
Catalyst used in middle embodiment 10.Gained polylactide is heterotactic polylactide after reaction, quality 1.33
G, yield 92.4%, molecular weight are 1.7 ten thousand, heterotactic stereoselectivityP r For 0.71.
Comparative example 4
Ligand structure formula such as formula used(A), wherein R1For methyl;R2For trifluoromethyl, reaction process is:Under nitrogen atmosphere, will
0.34 g of ligand A are dissolved in 10 mL drying hexamethylenes, and the triisopropylaluminiuand of ligand 1.05 times of moles of A is added at 0 DEG C,
After question response temperature is raised to room temperature naturally, heating reaction temperature to 50 DEG C of reactions 5 it is small when, added after reaction 47 microlitres of water stop it is anti-
Should, organic phase is collected in liquid separation, and anhydrous sodium sulfate drying, is spin-dried for solvent and obtains crude product, discovery obtains compound and do not change
(Isopropyl does not carry out C=O addition reactions).Triisopropylaluminiuand can not carry out addition reaction.
Comparative example 5
P-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into 1, the 3- propane diamine of p-methyl benzenesulfonic acid equimolar amounts, then add
Enter the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, heating reflux reaction, reaction is cooled to room temperature by solid after terminating
Filtering, washing, is dried to obtain solid.Solid is dissolved into dichloromethane, the saturated water of excessive sodium acid carbonate is slowly added dropwise
Solution, room temperature reaction, liquid separation after reaction, is dried with anhydrous magnesium sulfate, is spin-dried for solvent and is obtained unilateral phthalic anhydride guarantor
1, the 3- propane diamine of shield.The propane diamine of unilateral phthalic anhydride protection and the hexafluoroacetylacetone of equimolar amounts add in methyl alcohol
Heat reflux, reaction are put into refrigerator after terminating and cool down, and separate out solid, and filtering, is washed with cold methanol, dry, obtains chemical combination
Thing LD.
The preparation of Al catalysts:Under nitrogen atmosphere, 0.30 g of compound L D are dissolved in 10 mL dry toluenes, at -5 DEG C
The lower trimethyl aluminium for adding 1.1 times of compound L D moles, after question response temperature is raised to room temperature naturally, is heated to 100 DEG C of reactions 3
Hour, vacuum drains solvent after reaction terminates, and adds dry n-hexane washing, filtering, drying, obtains 0.27 g solids,
Yield 79.4%, the aluminium compound through hydrolysis after do mass spectral characteristi find such ligand can only unilateral generation addition reaction obtain
LDAlMe2(HRESI-MS: m/z cacld. C16H12F6N2O3 [M-H]-; 393.0676, found: 393.0670).
Method according to embodiment 13 prepares polylactide, unlike:Catalyst used is the Al catalysts.Reaction
The quality of products obtained therefrom is 0.66 g afterwards, and yield 45.8%, molecular weight is 1.1 ten thousand, no stereoselectivity.
Claims (10)
1. a kind of method of asymmetric aluminum complex catalysis lactide polymerization using the derivative containing acetylacetone,2,4-pentanedione, it is characterized in that bag
Include following steps:Catalyst, organic solvent, benzylalcohol co-catalyst and lactide are mixed, protected in anhydrous and oxygen-free and inert gas
Shield is lower to carry out ring-opening polymerization, carries out reactant after reaction to handle to obtain polylactide;The catalyst is containing acetylacetone,2,4-pentanedione
The asymmetric aluminum complex of derivative, its structural formula as shown in following formula I, wherein, R1It is preferably trifluoro for trifluoromethyl or methyl
Methyl, R2It is preferably phenyl for phenyl, trifluoromethyl or methyl;
。
2. according to the method described in claim 1, it is characterized in that:Method for preparing catalyst is:Ligand A or ligand II, which are added, to be had
In solvent, -10~0 oTrimethyl aluminium is added under C, reaction temperature is warmed to room temperature naturally after adding, then rises to temperature
30~110oC is reacted, and vacuum drains solvent, washing, filtering after reaction, obtains the derivative containing acetylacetone,2,4-pentanedione described in formula I
Asymmetric aluminum complex;Ligand A and II structural formula of ligand are as follows, wherein, R1It is trifluoromethyl or methyl, is preferably all trifluoro
Methyl, R2It is phenyl, trifluoromethyl or methyl, is preferably all phenyl;
。
3. according to the method described in claim 2, it is characterized in that:In catalyst preparation process, ligand A or ligand II and trimethyl
The molar ratio 1 of aluminium:1~1.3, preferably 1:1~1.05.
4. according to the method described in claim 2, it is characterized in that:In catalyst preparation process, the organic solvent is dry
One or both of hexane, toluene and hexamethylene;Consumption of organic solvent is 5~40 times of reaction raw materials gross mass.
5. according to the method described in claim 2, it is characterized in that:In catalyst preparation process, it is raised to after room temperature again by temperature
Rise to 30~110oC(It is preferred that 40~60oC)When reaction 1~12 is small, when preferably reaction 3~6 is small.
6. according to the method described in claim 2, it is characterized in that:In catalyst preparation process, react under inert gas shielding
Carry out.
7. according to the method any one of claim 1-6, it is characterized in that:During ring-opening polymerization, lactide and catalysis
The molar ratio of agent is 50~1500:1;The molar ratio of Bian alcohol co-catalyst and catalyst is 1~3:1.
8. according to the method any one of claim 1-6, it is characterized in that:During ring-opening polymerization, the organic solvent
For toluene or tetrahydrofuran.
9. according to the method any one of claim 1-6, it is characterized in that:During ring-opening polymerization, reaction temperature 20
~110 DEG C, the reaction time is 1-1440 minutes.
10. according to the method any one of claim 1-6, it is characterized in that:The lactide is rac-lactide, a left side
Revolve lactide or Study of Meso-Lactide.
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STUART L. HANCOCK ET AL: ""Aluminium salalen complexes based on 1,2-diaminocyclohexane and their exploitation for the polymerisation of rac-lactide"", 《DALTON TRANSACTIONS》 * |
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