CN107973743A - Four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base and its preparation method and application - Google Patents
Four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base and its preparation method and application Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 20
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 151
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 22
- -1 cyclic lactone Chemical group 0.000 claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 96
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 229940126062 Compound A Drugs 0.000 claims description 35
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 35
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 22
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 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 6
- 239000002994 raw material 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 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 64
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 63
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005406 washing Methods 0.000 description 65
- 239000000047 product Substances 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- 239000011261 inert gas Substances 0.000 description 31
- 235000019445 benzyl alcohol Nutrition 0.000 description 30
- 239000003708 ampul Substances 0.000 description 29
- 150000003938 benzyl alcohols Chemical class 0.000 description 29
- 229910001873 dinitrogen Inorganic materials 0.000 description 29
- 238000012869 ethanol precipitation Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000003808 methanol extraction Methods 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229920000747 poly(lactic acid) Polymers 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 8
- 150000003613 toluenes Chemical class 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- 229920000954 Polyglycolide Polymers 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 239000003863 metallic catalyst Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 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
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- 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
- C08G63/78—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)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base and its preparation method and application.The present invention provides a kind of four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base, which can be complexed to form complex with N, N, O, O quad-tree index with alkyl aluminum.Ligand structure of the present invention is special, preparation method is simple, the aluminum complex of formation can be as the catalyst of cyclic lactone ring-opening polymerization, catalytic activity is high, and stereoselectivity is high, and reaction rate is quickly, polymerisation is easy to operate, and can be controllable obtain the product of different molecular weight, selectivity is wide, there is good market prospects.
Description
Technical field
The present invention relates to four tooth nitrogen oxygen ligand of divalence and its preparation method and application, and in particular to four containing ethylenediamine base
Symmetrical ligand of tooth nitrogen oxygen and its preparation method and application.
Background technology
Due to the non-renewable of petroleum resources and using oil as white pollution caused by the conventional polymer material of raw material,
Conventional polymer material faces two hang-ups of energy crisis and environmental pollution, finds the renewable resource instead of oil, exploitation
Environmentally friendly, biodegradation type new material becomes the trend of following macromolecule polymeric material development.Polyester conduct can give birth to
Thing it is compatible and can the high molecular material of biodegradable environmental type have been to be concerned by more and more people.In natural life cycle
In border or in organism, polyester material can thoroughly resolve into water and carbon dioxide.Polyester is nontoxic, nonirritant, and has
Good biocompatibility, therefore it is widely used in biomedical and packaging material, such as operation suture thread, packaging, medicine
Control release and tissue engineering bracket etc..What the excellent biocompatibility of polyester, biological degradability and sustainable development utilized
Performance, makes it have become 21 century most promising high molecular material.
Polyester material can directly be obtained from corresponding monomer acids with polycondensation method or should with homogeneous catalyst catalytic phase
Monomer ring-opening polymerisation obtain, most effective and common method be with metallic catalyst catalysis monomer ring-opening polymerisation obtain accordingly
Polyester.Due to the catalytic effect that metallic catalyst is excellent, the molecular weight and molecualr weight distribution of polymerization can be effectively controlled, it is various each
The metallic catalyst of sample is prepared out the ring-opening polymerization catalyst as cyclic lactone monomer, and most common metallic catalyst is gold
The metal complex catalysts that category center and ligand are formed.In metal complex catalysts, the selection of ligand and metal for
The speed of ring-opening polymerization, the performance of products obtained therefrom are all very crucial, in the case of same metal, the often replacement of ligand
Unexpected catalytic effect can be shown with selection, therefore selects the research of the ligand of different structure to be also subject to that people's is extensive
Concern.
The content of the invention
The present invention provides a kind of four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base, which is nitrogen, oxygen quad-tree index,
Complex can be formed with alkyl aluminum, gained complex has good catalytic activity in cyclic lactone ring-opening polymerization.
Present invention also offers the preparation method of the four symmetrical ligands of tooth nitrogen oxygen for containing ethylenediamine base, this method prepares letter
It is single, it is easy to accomplish.
Present invention also offers this to contain the four symmetrical ligands of tooth nitrogen oxygen of ethylenediamine base as cyclic lactone ring-opening polymerization
Catalyst ligand application and the ligand made of cyclic lactone ring-opening polymerization catalyst.
The present invention is in the young project of National Nature fund committee（No 21104026）Subsidy under complete, skill of the present invention
Art scheme is as follows：
The present invention provides a kind of four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base, have the structural formula as shown in following formula II,
The ligand can be referred to as ligand II or compound ii：
。
In above-mentioned formula II, it is contemplated that steric hindrance, the substituent R select C1-C6 straight chained alkyl, such as methyl, ethyl,
N-propyl, normal-butyl, n-pentyl, n-hexyl.When selecting these groups, which can be readily synthesized, if selecting other
Group, ligand form difficulty or can not obtain.R is preferably methyl, ethyl or n-hexyl, is most preferably n-hexyl.
The present invention provides the preparation method of the above-mentioned four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base, including following step
Suddenly：Compound A is added in organic solvent, -10~0 oTrialkylaluminium is added under C, reaction temperature is risen to naturally after adding
Room temperature, then rises to 30~110 by temperatureoC is reacted, and is reacted in backward reaction solution and is added water, is stood and is divided after being sufficiently mixed
Liquid, collects organic phase obtained by liquid separation, recycles organic solvent, obtains crude product, crude product is recrystallized, obtain containing shown in formula II
There are the four symmetrical ligands of tooth nitrogen oxygen of ethylenediamine base（That is ligand II）.
The preparation method reaction equation of above-mentioned ligand II is as follows, and compound A first forms aluminum complex, gained with alkyl reactive aluminum
Aluminum complex is broken water sensitive, in the presence of water Al-O keys, is hydrolyzed into ligand II and Al (OH)3, ligand II, which enters, to be had
In machine phase, it can be obtained by liquid separation, recycling design：
In above-mentioned II preparation method of ligand, the preparation method of compound A is shown in formula A：Phthalic anhydride is dissolved into acetic acid
In solution, the ethylenediamine of 0.5 times of mole of phthalic anhydride is added, heating carries out back flow reaction, and reaction will be anti-after terminating
Answer liquid to be poured into water, separate out crystal, filtering, washing, obtain compound A after separating out completely.
In above-mentioned II preparation method of ligand, the molecular formula of the trialkylaluminium is AlR3, wherein alkyl R is the straight of C1-C6
Alkyl group, is preferably methyl, ethyl or n-hexyl, i.e. trialkylaluminium is preferably trimethyl aluminium, triethyl aluminum, tri-n-hexyl aluminum.
When R selects these groups, which can be readily synthesized, if selection other groups, ligand II formed it is difficult or
It can not obtain.
In above-mentioned II preparation method of ligand, the molar ratio 1 of compound A and trialkylaluminium：1~1.3, preferably 1：1~1.05.
In above-mentioned II preparation method of ligand, the organic solvent is dry hexane, toluene and one kind in hexamethylene or
Two kinds, preferably dry hexane or toluene.
In above-mentioned II preparation method of ligand, consumption of organic solvent is reaction raw materials（Compound A and trialkylaluminium）Gross mass
5~40 times.
In above-mentioned II preparation method of ligand, 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, is preferably raised to 40~60oC is reacted.30~
110oC（It is preferred that 40~60oC）When the time reacted is 1~12 small, when being preferably 3~6 small.
In above-mentioned II preparation method of ligand, react and carried out under gas shield, the gas is inert gas or nitrogen.
In above-mentioned II preparation method of ligand, after reaction, water is added into reaction solution, liquid separation is stood after being sufficiently mixed.
The dosage of water is the mole of 3 times or so of compound A.After standing liquid separation, gained organic phase is spin-dried for solvent, and remaining crude product is used
One or both of methanol, ethanol are recrystallized, you can obtain II ligand product of formula.
The compounds of this invention A and ligand II can be formed aluminium with alkyl reactive aluminum and be matched somebody with somebody with N, N, O, O quad-tree index
Compound, gained aluminum complex structural formula is as shown in following formula I, in formula I, R be C1-C6 straight chained alkyl, be preferably methyl, ethyl or
N-hexyl, is most preferably n-hexyl：
。
The aluminum complex that ligand of the present invention is formed with alkyl aluminum can be used as the catalyst of cyclic lactone ring-opening polymerization, its
The open loop of a variety of cyclic lactones such as rac-lactide, Study of Meso-Lactide, levorotatory lactide, caprolactone, glycolide can be catalyzed
Polymerization.During the catalyst cyclic lactone ring-opening polymerization, have catalytic activity is high, stereoselectivity is good, reaction rate is fast,
The advantages that molecular weight controllability is high, particularly can obtain the high isotactic poly of fusing point when being catalyzed rac-lactide polymerization
Lactide, shows higher stereoselectivity, and stereoselectivity reaches as high as 0.81.In catalysis lactide, caprolactone and second
During lactide, obtained polymer is the polymer of benzyloxy end-blocking.Therefore, the four tooth nitrogen oxygen of the invention containing ethylenediamine base are symmetrical
Ligand as the ligand of the catalyst of cyclic lactone ring-opening polymerization application also within the scope of the present invention.
When aluminum complex of the present invention is used as the catalyst of cyclic lactone ring-opening polymerization, with carbon number in substituent R
Increase, the stereoselectivity of catalyst has elevated trend, and catalytic activity has the trend of reduction.
Aluminum complex shown in above-mentioned formula I, can be prepared as the ligand shown in formula II with alkyl aluminum, can also be used and be changed
Compound A is made with alkyl reactive aluminum, its specific preparation method comprises the following steps：Compound A or ligand II are added organic
In solvent, -10~0 oTrialkylaluminium is added under C, reaction temperature is warmed to room temperature naturally after adding, temperature is then risen to 30
~110oC is reacted, and vacuum drains solvent, washing, filtering after reaction, obtains the complex described in formula I.Reaction equation is as follows：
In above-mentioned aluminum complex preparation method, the molecular formula of the trialkylaluminium is AlR3, wherein alkyl R is the straight chain of C1-C6
Alkyl, is preferably methyl, ethyl or n-hexyl, i.e. trialkylaluminium is preferably trimethyl aluminium, triethyl aluminum, tri-n-hexyl aluminum.
In above-mentioned aluminum complex preparation method, compound A or ligand and the molar ratio 1 of trialkylaluminium shown in formula II：1~
1.3, preferably 1：1~1.05.
In above-mentioned aluminum complex preparation method, the organic solvent is one kind in dry hexane, toluene and hexamethylene
Or two kinds, it is preferably hexane or toluene.Consumption of organic solvent is reaction raw materials（Compound A or ligand and three alkane shown in formula II
Base aluminium）5~40 times of gross mass.
In above-mentioned aluminum complex preparation method, reaction nature rises to 30~110 again after being raised to room temperatureoC is reacted, example
Such as 30oC、40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC, is preferably raised to 40~60oC is reacted.30~
110oC（It is preferred that 40~60oC）When the time reacted is 1~12 small, when being preferably 3~6 small.
In above-mentioned aluminum complex preparation method, react and carried out under gas shield, the gas is inert gas or nitrogen.
After reaction solution is spin-dried for solvent, residue is washed with n-hexane, is then dried, you can obtains the aluminum complex described in formula I.
When using the aluminum complex described in formula I as catalyst, cyclic lactone ring-opening polymerization specifically includes following steps：Will
Aluminum complex, organic solvent, alcohol co-catalyst and cyclic lactone mixing described in formula I, carry out under anhydrous and oxygen-free and gas shield
Ring-opening polymerization, is handled reactant after reaction, obtains polylactone.
In above-mentioned ring-opening polymerization, cold methanol or ethanol purification polylactone are added after reaction, obtains polylactone after purification.
In above-mentioned ring-opening polymerization, organic solvent used in reaction is toluene or tetrahydrofuran, preferably toluene.Used in reaction
Alcohol co-catalyst is benzylalcohol.
In above-mentioned ring-opening polymerization, the molar ratio of cyclic lactone and catalyst is 50~1500：1, such as 50:1、100：1、
200:1、300:1、400:1、500:1、600：1、800:1、1000:1、1200:1、1500：1.Alcohol co-catalyst and catalyst
Molar ratio 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 up to 0.65, and when reaction temperature is at 20 DEG C, stereoselectivity when being catalyzed to rac-lactide is reachable
0.81。
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..
The present invention provides a kind of four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base, which can be with tetra- tooth of N, N, O, O
Coordination, is complexed to form aluminum complex with alkyl aluminum.Ligand structure of the present invention is special, and preparation method is simple, the aluminum complex of formation
Can be as the catalyst of cyclic lactone ring-opening polymerization, catalytic activity is high, and stereoselectivity is high, and reaction rate quickly, polymerize
Operation is simple, and can be controllable obtain the product of different molecular weight, selectivity is wide, there is good market prospects.
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 four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base
According to following route synthesis types（Ⅱ）Shown ligand.
The preparation method of compound A is：Phthalic anhydride is dissolved into acetic acid solution（Concentration 36-38wt%）In, add
The ethylenediamine of 0.5 times of mole of phthalic anhydride, be heated to reflux 8 it is small when, reaction terminate after reaction solution is poured into water, make
Crystal separates out, and filtering, washing, obtain white crystal after precipitation completely, as compound A, yield 96%.
Embodiment 1
In a nitrogen atmosphere, 0.43 g of compound A are dissolved in 10 mL dry toluenes, 1.0 times of compounds is added at -10 DEG C
The trimethyl aluminium of A moles, after question response temperature is raised to room temperature naturally, be heated to 90 DEG C reaction 3 it is small when, reaction terminate after,
In room temperature slowly toward the water of 73 microlitres of dropwise addition in reaction solution, liquid separation is stood after being thoroughly mixed, organic phase is collected, is spin-dried for molten
Agent, obtains crude product, by crude product through recrystallizing methanol, obtains 0.39 g of net product, yield 82.5%.
Products obtained therefrom is characterized, it is as a result as follows：
Elemental analysis result： C, 68.12; H, 5.74; N, 7.97 %.
1H NMR (400 MHz, CDCl3) δ7.76 (d, J = 7.2 Hz, 2H, Ar–H), 7.38 (m, 6H,
Ar–H), 3.64 (s, 4H, NCH 2), 1.65 (s, 6H, CCH 3).
HRESI-MS: m/z cacld. C20H20N2O4 [M-H]-; 351.1344, found: 351.1346.
Structure of title compound formula such as above formula is can be seen that from above characterization result（Ⅱ）Shown, R is methyl.
Embodiment 2
In a nitrogen atmosphere, 0.40 g of compound A are dissolved in 15 mL drying hexamethylenes, 1.05 times of chemical combination is added at 0 DEG C
The triethyl aluminum of thing A moles, after question response temperature is raised to room temperature naturally, be heated to 60 DEG C reaction 10 it is small when, added after reaction
In room temperature slowly toward the water of 68 microlitres of dropwise addition in reaction solution, liquid separation is stood after being thoroughly mixed, organic phase is collected, is spin-dried for molten
Agent, obtains crude product, by crude product through recrystallizing methanol, obtains 0.40 g of net product, yield 84.2%.
Products obtained therefrom is characterized, it is as a result as follows：
Elemental analysis result： C, 69.50; H, 6.31; N, 7.41 %.
1H NMR (400 MHz, CDCl3) δ 7.77(d, 1H, J = 7.2 Hz, Ar–H), 7.36 (m, 6H,
Ar–H), 3.63 (s, 4H, NCH 2), 2.04 (q, J = 7.0 Hz, 4H, CH 2CH3), 1.04 (t, J =7.0
Hz, 6H, CH2CH 3)。
HRESI-MS: m/z cacld. C22H24N2O4 [M-H]-; 379.1660, found: 379.1662.
Structure of title compound formula such as above formula is can be seen that from above characterization result（Ⅱ）Shown, R is ethyl.
Embodiment 3
Under nitrogen atmosphere, 0.40 g of compound A are dissolved in 10 mL dry toluenes, 1.1 times of compound A is added at -5 DEG C and are rubbed
You amount tri-n-hexyl aluminum, after question response temperature is raised to room temperature naturally, be heated to 50 DEG C reaction 8 it is small when, reaction terminate after add
Enter in room temperature slowly toward the water of 68 microlitres of dropwise addition in reaction solution, liquid separation is stood after being thoroughly mixed, organic phase is collected, is spin-dried for molten
Agent, obtains crude product, by crude product through ethyl alcohol recrystallization, obtains 0.48 g of net product, yield 78.0%.
Products obtained therefrom is characterized, it is as a result as follows：
Elemental analysis result： C, 73.15; H, 8.21; N, 5.72%.
1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.1 Hz, 2H, Ar–H), 7.37 (m, 6H,
Ar–H), 3.62 (s, 4H, NCH 2), 1.96 (m, 4H, CH2CH 2), 1.31(m, 16H, CH2CH 2), 0.94 (m,
6H, CH2CH 3).
HRESI-MS: m/z cacld. C34H45N2O4 [M-H]-; 545.3376, found: 545.3372.
Structure of title compound formula such as above formula is can be seen that from above characterization result（Ⅱ）Shown, R is n-hexyl.
Embodiment 4
In a nitrogen atmosphere, 0.40 g of compound A are dissolved in 15 mL drying hexanes, 1.3 times of compound A is added at 0 DEG C
The tri-butyl aluminum of mole, after question response temperature is raised to room temperature naturally, be heated to 40 DEG C of reactions 12 it is small when, added after reaction 68 micro-
The water risen, stands liquid separation after being thoroughly mixed, collect organic phase, be spin-dried for solvent, obtain crude product, crude product is tied again through methanol
Crystalline substance, obtains 0.39 g of net product, yield 79.6%.Verified through nuclear-magnetism, structure of title compound formula such as above formula（Ⅱ）Shown, R is positive fourth
Base.
Using compound A as I aluminum complex of raw material formula
Embodiment 5
In a nitrogen atmosphere, 0.32 g of compound A are dissolved in 10 mL drying hexanes, 1.0 times of compounds is added at -10 DEG C
The trimethyl aluminium of A moles, after question response temperature is raised to room temperature naturally, be heated to 50 DEG C reaction 6 it is small when, reaction terminate after very
Empty concentrated solvent, filters and is washed with dry n-hexane, collects and drying is weighed, obtain 0.32 g solids, yield 81.6%.
Products therefrom nuclear-magnetism information is as follows, and can be seen that I aluminum complex of formula that R is methyl from nuclear-magnetism information synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ7.80 (d, J = 7.4 Hz, 2H, Ar–H), 7.42 (m, 6H,
Ar–H), 3.67 (s, 4H, NCH 2), 1.59 (s, 6H, CCH 3), –0.47(s, 3H, AlCH3). Anal.
Calcd for C21H21AlN2O4: C 64.28, H 5.39, N 7.14. Found: C 64.23, H 5.32, N
7.15.
Embodiment 6
Under nitrogen atmosphere, 0.43 g of compound A are dissolved in 15 mL drying hexamethylenes, 1.05 times of compound A is added at 0 DEG C
The triethyl aluminum of mole, after question response temperature is raised to room temperature naturally, heating reaction temperature to 60 DEG C reaction 4 it is small when, reaction knot
Shu Yihou vacuum drains solvent, adds dry n-hexane lotion, then filters, is dry, obtaining 0.47 g solids, yield
80.6%。
Products therefrom nuclear-magnetism information is as follows, and can be seen that I aluminum complex of formula that R is ethyl from nuclear-magnetism information synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 7.78(d, 1H, J = 7.1 Hz, Ar–H), 7.40 (m, 6H,
Ar–H), 3.65 (m, 4H, NCH 2), 2.04 (q, J = 6.7 Hz, 4H, CH 2CH3), 1.35 (q, 2H, J =
6.4 Hz, AlCH 2CH3), 1.04 (t, 6H, J = 6.7 Hz, CH2CH 3), 0.60 (t, 3H, J = 6.4 Hz,
AlCH2CH 3). Anal. Calcd for C24H27AlN2O4: C 66.35, H 6.26, N 6.45. Found: C
66.34, H 6.30, N 6.46.
Embodiment 7
Under nitrogen atmosphere, 0.30 g of compound A are dissolved in 9 mL dry toluenes, 1.1 times of compound A is added at -5 DEG C and are rubbed
You amount tri-n-hexyl aluminum, after question response temperature is raised to room temperature naturally, be heated to 90 DEG C reaction 2 it is small when, reaction terminate after very
Sky drains solvent, adds dry n-hexane washing, filtering, drying, obtains 0.39 g solids, yield 69.1%.
The nuclear-magnetism information of products obtained therefrom is as follows, it can be seen that R be n-hexyl I aluminum complex of formula synthesis into
Work(.
1H NMR (400 MHz, CDCl3) δ 7.77 (d, J = 7.3 Hz, 2H, Ar–H), 7.40 (m, 6H,
Ar–H), 3.67 (s, 4H, NCH 2), 1.94 (m, 4H, CH2CH 2), 1.36(m, 10H, CH2CH 2), 1.24 (m,
16H, CH2CH 2), 0.97 (m, 9H, CH2CH 3). Anal. Calcd for C36H51AlN2O4: C 71.73, H
8.53, N 4.65. Found: C 71.76, H 8.57, N 4.69.
Embodiment 8
In a nitrogen atmosphere, 0.23 g of compound A are dissolved in 8 mL dry toluenes, 1.0 times of compound A is added at -10 DEG C
Three n-butylaluminums of mole, 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
Solvent is concentrated in vacuo, filters and is washed with dry n-hexane, collects and drying is weighed, obtain 0.31 g solids, yield 83.4%.
Structure of title compound formula such as above formula（I）Shown, R is normal-butyl.
With formula（Ⅱ）Ligand is I aluminum complex of raw material formula
Embodiment 9
Ligand structure formula such as above formula used（II）, R is methyl, and reaction process is：In a nitrogen atmosphere, 0.30 g of ligand is dissolved in
In 10 mL drying hexanes, the trimethyl aluminium of 1.0 times of ligand moles is added at -10 DEG C, question response temperature is raised to room temperature naturally
Afterwards, be heated to 40 DEG C reaction 8 it is small when, reaction terminate after be concentrated in vacuo solvent, filter simultaneously with drying n-hexane wash, drying
Weigh to obtain 0.30 g solids, yield 90%, for product structure formula as shown in formula I, R is methyl.
Embodiment 10
Ligand structure formula such as above formula used（II）, R is ethyl, and reaction process is：Under nitrogen atmosphere, 0.35 g of ligand is dissolved in 10
In mL drying hexamethylenes, the triethyl aluminum of 1.05 times of ligand moles is added at 0 DEG C, question response temperature is raised to room temperature naturally
Afterwards, heat reaction temperature to 50 DEG C reaction 5 it is small when, reaction terminate after vacuum drain solvent, add dry n-hexane and wash
Wash, filter, collect and drying weighs to obtain 0.33 g solids, yield 86%, for product structure formula as shown in formula I, R is ethyl.
Embodiment 11
Ligand structure formula such as above formula used（II）, R is butyl, and reaction process is：Under nitrogen atmosphere, 0.40 g of ligand is dissolved in 15
In mL dry toluenes, the tri-butyl aluminum of 1.1 times of ligand moles is added at -5 DEG C, after question response temperature is raised to room temperature naturally,
Be heated to 90 DEG C of reactions 2 it is small when, vacuum drains solvent after reaction terminates, and adds dry n-hexane washing, filtering, collection
And drying weighs to obtain 0.44 g solids, yield 81.5%, for product structure formula as shown in formula I, R is butyl.
Prepare polycaprolactone
Embodiment 12
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, R are methyl）, 10 μm of ol benzylalcohols, 20 mL tetrahydrofurans and 10
The caprolactone of mmol, then heats to 60oC, reaction add a small amount of water and terminate reaction after 8 minutes, with ethanol precipitation, washing number
It is secondary, it is dried in vacuo at room temperature, obtains 1.11 grams of products, yield 97.4%, molecular weight 33.7 ten thousand.
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, R are ethyl）, 100 μm of ol benzylalcohols, 10 mL toluene and 10
The caprolactone of mmol, is subsequently placed in 110oIn the oil bath of C, reaction adds a small amount of water and terminates reaction after 1.5 minutes, sunk with ethanol
Form sediment, washing for several times, be dried in vacuo at room temperature, obtain 1.12 grams, yield 98.2%, molecular weight 1.7 ten thousand.
Embodiment 14
Method according to embodiment 13 prepares polycaprolactone, unlike：Catalyst used is that aluminum complex, R shown in formula I are
N-hexyl.The quality of products obtained therefrom is 1.08 g after reacting 2 minutes, and yield 94.6%, molecular weight is 1.4 ten thousand.
Embodiment 15
Method according to embodiment 13 prepares polycaprolactone, unlike：Catalyst used is that aluminum complex, R shown in formula I are
Methyl.The quality of products obtained therefrom is 1.09 g after reacting 1 minute, and yield 95.6%, molecular weight is 1.5 ten thousand.
Embodiment 16
Method according to embodiment 13 prepares polycaprolactone, unlike：Catalyst used is that aluminum complex, R shown in formula I are
Normal-butyl.The quality of products obtained therefrom is 1.10 g after reacting 1.7 minutes, and yield 96.5%, molecular weight is 1.6 ten thousand.
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, R are methyl）, 100 μm of ol benzylalcohols, 10 mL toluene and 10 mmol
Caprolactone, then respectively 20oC、40oC、60oC、80oC and 100oReacted under C, add a small amount of water after reaction and terminate instead
Should, with methanol extraction, washing for several times, it is dried in vacuo at room temperature.
Wherein, reacted 40 minutes at 20 DEG C, obtain 1.10 grams of products, yield 96.5%, molecular weight 1.8 ten thousand.
Reacted 15 minutes at 40 DEG C, obtain 1.09 grams of products, yield 95.6%, molecular weight 2.0 ten thousand.
Reacted 10 minutes at 60 DEG C, obtain 1.11 grams of products, yield 97.4%, molecular weight 2.1 ten thousand.
Reacted 3 minutes at 80 DEG C, obtain 1.08 grams of products, yield 94.7%, molecular weight 1.9 ten thousand.
Reacted 1.5 minutes at 100 DEG C, obtain 1.12 grams of products, yield 98.2%, molecular weight 1.8 ten thousand.
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 20 μm of ol catalyst（Aluminum complex shown in formula I, R are n-hexyl）, 20 μm of ol benzylalcohols, 8 mL toluene and 2 mmol
Caprolactone, then 20oC reactions add a small amount of water and terminate reaction after sixty minutes, with ethanol precipitation, washing for several times, at room temperature very
Sky is dry, obtains 0.22 gram, yield 96.5%, molecular weight 1.7 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 20 μm of ol catalyst（Aluminum complex shown in formula I, R are ethyl）, 20 μm of ol benzylalcohols, 15 mL tetrahydrofurans and 4
The caprolactone of mmol, then heats to 50oC reacts, and reaction adds a small amount of water and terminates reaction after 15 minutes, with ethanol precipitation, wash
Wash for several times, be dried in vacuo at room temperature, obtain 0.43 gram, yield 94.3%, molecular weight 3.3 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, R are ethyl）, 20 μm of ol benzylalcohols, 20 mL toluene and 5 mmol
Caprolactone, is subsequently placed in 70oIn the oil bath of C, reaction adds a small amount of water and terminates reaction after ten minutes, with methanol extraction, washing number
It is secondary, it is dried in vacuo at room temperature, obtains 0.53 gram, yield 93.0%, molecular weight 4.5 ten thousand.
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, R are n-hexyl）, 30 μm of ol benzylalcohols, 20 mL toluene and 6 mmol
Caprolactone, be subsequently placed in 80oIn the oil bath of C, reaction adds a small amount of water and terminates reaction after 9 minutes, with methanol extraction, washing number
It is secondary, it is dried in vacuo at room temperature, obtains 0.65 gram, yield 95.0%, molecular weight 4.6 ten thousand.
Embodiment 22
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, R are n-hexyl）, 20 μm of ol benzylalcohols, 20 mL toluene and 15mmol
Caprolactone, be subsequently placed in 30oIn the oil bath of C, reaction adds a small amount of water and terminates reaction after 30 minutes, with methanol extraction, washing
For several times, it is dried in vacuo at room temperature, obtains 1.63 grams, yield 95.3%, molecular weight 11.4 ten thousand.
Embodiment 23
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, R are ethyl）, 100 μm of ol benzylalcohols, 10 mL toluene and 5mmol
Caprolactone, be subsequently placed in 70oIn the oil bath of C, reaction adds a small amount of water and terminates reaction after 9 minutes, with methanol extraction, washing number
It is secondary, it is dried in vacuo at room temperature, obtains 0.55 gram, yield 96.5%, molecular weight 0.6 ten thousand.
Prepare polylactide
Embodiment 24
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, R are methyl）, 10 μm of ol benzylalcohols, 8 mL toluene and 2 mmol a left side
Lactide is revolved, is subsequently placed in 110oIn the oil bath of C, when reaction 1 is small 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 0.28 gram, yield 97.2%, molecular weight 7.8 ten thousand.
Embodiment 25
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 50 μm of ol catalyst（Aluminum complex shown in formula I, R are methyl）, 50 μm of ol benzylalcohols, 10 mL toluene and 5 mmol
Rac-lactide, then 20oA small amount of water, which is added, after when C reactions 22 are small terminates reaction, with ethanol precipitation, washing for several times, room temperature
Lower vacuum drying, obtains 0.71 gram, yield 98.6%.Products therefrom is isotaxy polylactide, molecular weight 1.9 ten thousand, Quan Tongli
Structure stereoselectivityP m= 0.78。
Embodiment 26
Method according to embodiment 25 prepares polylactide, unlike：Catalyst used is that aluminum complex, R shown in formula I are
Ethyl.React 23 it is small when after the quality of products obtained therefrom be 0.69 g, yield 95.8%, molecular weight is 2.1 ten thousand, isotaxy
StereoselectivityP m= 0.79。
Embodiment 27
Method according to embodiment 25 prepares polylactide, unlike：Catalyst used is that aluminum complex, R shown in formula I are
Normal-butyl.React 23.5 it is small when after the quality of products obtained therefrom be 0.70 g, yield 97.2%, molecular weight is 2.3 ten thousand, Quan Tong
Vertical structure stereoselectivityP m= 0.80。
Embodiment 28
Method according to embodiment 25 prepares polylactide, unlike：Catalyst used is that aluminum complex, R shown in formula I are
N-hexyl.React 24 it is small when after the quality of products obtained therefrom be 0.68 g, yield 94.4%, molecular weight is 2.0 ten thousand, Quan Tongli
Structure stereoselectivityP m= 0.81。
Embodiment 29
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 50 μm of ol catalyst（Aluminum complex shown in formula I, R are n-hexyl）, 50 μm of ol benzylalcohols, 10 mL toluene and 5 mmol
Rac-lactide, then respectively 40oC、60oC and 80oReacted under C, add a small amount of water after reaction and terminate reaction, use
Methanol extraction, washing for several times, are dried in vacuo at room temperature.
Wherein, when 40 DEG C of reactions 20 are small, 0.70 gram of product is obtained, yield 97.2%, molecular weight 2.4 ten thousand,P m = 0.74。
When 60 DEG C of reactions 14 are small, 0.71 gram of product is obtained, yield 98.6%, molecular weight 2.5 ten thousand,P m = 0.70。
When 80 DEG C of reactions 12 are small, 0.68 gram of product is obtained, yield 94.4%, molecular weight 2.0 ten thousand,P m = 0.65。
Embodiment 30
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 25 μm of ol catalyst（Aluminum complex shown in formula I, R are methyl）, 50 μm of ol benzylalcohols, 8 mL toluene and 5 mmol a left side
Lactide is revolved, is subsequently placed in 70oIn the oil bath of C, when reaction 12 is small 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 0.69 gram, yield 95.8%, molecular weight 5.8 ten thousand.
Embodiment 31
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, R are ethyl）, 30 μm of ol benzylalcohols, 5 mL tetrahydrofurans and 3 mmol
Study of Meso-Lactide, then 30oA small amount of water, which is added, after when C reactions 20 are small terminates reaction, with ethanol precipitation, washing for several times, room
The lower vacuum drying of temperature, obtains 0.42 gram, yield 97.2%, molecular weight 8.7 ten thousand.
Embodiment 32
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, R are methyl）, 10 μm of ol benzylalcohols, 8 mL toluene and 4 mmol it is interior
Meso-lactide, is subsequently placed in 90oIn the oil bath of C, when reaction 10 is small after add a small amount of water and terminate reaction, with ethanol precipitation, wash
Wash for several times, be dried in vacuo at room temperature, obtain 0.56 gram, yield 97.2%, molecular weight 8.4 ten thousand.
Embodiment 33
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, R are ethyl）, 20 μm of ol benzylalcohols, 10 mL toluene and 12 mmol
Study of Meso-Lactide, is subsequently placed in 70oIn the oil bath of C, when reaction 12 is small after add a small amount of water and terminate reaction, with ethanol precipitation,
Washing for several times, is dried in vacuo at room temperature, obtains 1.64 grams, yield 94.9%, molecular weight 13.2 ten thousand.
Embodiment 34
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, R are n-hexyl）, 20 μm of ol benzylalcohols, 10 mL toluene and 10 mmol
Levorotatory lactide, then 100oA small amount of water, which is added, after when C reactions 4 are small terminates reaction, with ethanol precipitation, washing for several times, room temperature
Lower vacuum drying, obtains 1.35 grams, yield 93.8%, molecular weight 19.3 ten thousand.
Embodiment 35
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 150 μm of ol catalyst（Aluminum complex shown in formula I, R are ethyl）, 150 μm of ol benzylalcohols, 10 mL toluene and 15mmol
Levorotatory lactide, be subsequently placed in 50oIn the oil bath of C, when reaction 10 is small after add a small amount of water and terminate reaction, with ethanol precipitation,
Washing for several times, is dried in vacuo at room temperature, obtains 2.04 grams, yield 94.4%, molecular weight 2.4 ten thousand.
Embodiment 36
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, R are methyl）, 20 μm of ol benzylalcohols, 20 mL toluene and 15 mmol
Levorotatory lactide, then 110oA small amount of water is added after when C reactions 1 are small and terminates reaction, with ethanol precipitation, washing for several times, at room temperature
Vacuum drying, obtains 2.13 grams, yield 98.6%, molecular weight 24.2 ten thousand.
Prepare polyglycolide
Embodiment 37
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, R are methyl）, 10 μm of ol benzylalcohols, 8 mL toluene and 2 mmol second
Lactide, is subsequently placed in 110oIn the oil bath of C, reaction adds a small amount of water and terminates reaction after ten minutes, with ethanol precipitation, washing number
It is secondary, it is dried in vacuo at room temperature, obtains 0.22 gram, yield 94.8%, molecular weight 3.3 ten thousand.
Embodiment 38
Polyglycolide is prepared according to the method for embodiment 37, unlike：Catalyst used is that aluminum complex, R shown in formula I are
Ethyl.Reaction adds a small amount of water and terminates reaction after 12 minutes, with ethanol precipitation, washing for several times, be dried in vacuo at room temperature, obtain 0.23
Gram, yield 99.1%, molecular weight 3.4 ten thousand.
Embodiment 39
Polyglycolide is prepared according to the method for embodiment 37, unlike：Catalyst used is that aluminum complex, R shown in formula I are
Normal-butyl.Reaction adds a small amount of water and terminates reaction after 14 minutes, with ethanol precipitation, washing for several times, be dried in vacuo, obtain at room temperature
0.22 gram, yield 94.8%, molecular weight 3.1 ten thousand.
Embodiment 40
Polyglycolide is prepared according to the method for embodiment 37, unlike：Catalyst used is that aluminum complex, R shown in formula I are
N-hexyl.Reaction adds a small amount of water and terminates reaction after 15 minutes, with ethanol precipitation, washing for several times, be dried in vacuo, obtain at room temperature
0.21 gram, yield 90.5%, molecular weight 3.2 ten thousand.
Embodiment 41
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 50 μm of ol catalyst（Aluminum complex shown in formula I, R are methyl）, 50 μm of ol benzylalcohols, 20 mL toluene and 5 mmol
Glycolide, then respectively 20oC、40oC、60oC、80oC and 100oReacted under C, add a small amount of water after reaction and terminate reaction,
With methanol extraction, washing for several times, it is dried in vacuo at room temperature.
Wherein, when 20 DEG C of reactions 23 are small, 0.53 gram of product, yield 91.4%, molecular weight 3.1 ten thousand are obtained.
When 40 DEG C of reactions 10 are small, 0.54 gram of product, yield 93.1%, molecular weight 3.0 ten thousand are obtained.
When 60 DEG C of reactions 6 are small, 0.55 gram of product, yield 94.8%, molecular weight 3.3 ten thousand are obtained.
When 80 DEG C of reactions 1 are small, 0.54 gram of product, yield 93.1%, molecular weight 2.9 ten thousand are obtained.
When 100 DEG C of reactions 0.5 are small, 0.56 gram of product, yield 96.6%, molecular weight 3.1 ten thousand are obtained.
Embodiment 42
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, R are ethyl）, 100 μm of ol benzylalcohols, 20 mL tetrahydrofurans and 5
The glycolide of mmol, then 20oA small amount of water, which is added, after when C reactions 20 are small terminates reaction, with methanol extraction, washing for several times, room temperature
Lower vacuum drying, obtains 0.57 gram, yield 98.3%, molecular weight 0.5 ten thousand.
Embodiment 43
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, R are n-hexyl）, 20 μm of ol benzylalcohols, 20 mL toluene and 10
The glycolide of mmol, is subsequently placed in 50oIn the oil bath of C, when reaction 10 is small after add a small amount of water and terminate reaction, with ethanol precipitation,
Washing for several times, is dried in vacuo at room temperature, obtains 1.10 grams, yield 94.8%, molecular weight 18.2 ten thousand.
Embodiment 44
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, R are ethyl）, 10 μm of ol benzylalcohols, 30 mL toluene and 15 mmol
Glycolide, is subsequently placed in 70oIn the oil bath of C, when reaction 5 is small after add a small amount of water and terminate reaction, with methanol extraction, washing number
It is secondary, it is dried in vacuo at room temperature, obtains 1.67 grams, yield 96.0%, molecular weight 33.4 ten thousand.
Embodiment 45
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, R are n-hexyl）, 20 μm of ol benzylalcohols, 10 mL toluene and 3 mmol
Glycolide, be subsequently placed in 90oIn the oil bath of C, when reaction 1 is small after add a small amount of water and terminate reaction, with methanol extraction, washing number
It is secondary, it is dried in vacuo at room temperature, obtains 0.33 gram, yield 94.8%, molecular weight 3.3 ten thousand.
Embodiment 46
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, R are ethyl）, 30 μm of ol benzylalcohols, 10 mL tetrahydrofurans and 5
The glycolide of mmol, is subsequently placed in 50oIn the oil bath of C, when reaction 5 is small after add a small amount of water and terminate reaction, with methanol extraction, wash
Wash for several times, be dried in vacuo at room temperature, obtain 0.56 gram, yield 96.6%, molecular weight 2.9 ten thousand.
Embodiment 47
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, R are n-hexyl）, 20 μm of ol benzylalcohols, 20 mL toluene and 6 mmol
Glycolide, is subsequently placed in 70oIn the oil bath of C, when reaction 4 is small after add a small amount of water and terminate reaction, with methanol extraction, washing number
It is secondary, it is dried in vacuo at room temperature, obtains 0.67 gram, yield 96.3%, molecular weight 6.3 ten thousand.
Comparative example 1
The preparation of Raney nickel：Ligand structure formula such as above formula used（II）, R is methyl, and reaction process is：0.30 g of ligand is molten
In 10 mL absolute ethyl alcohols, at room temperature add 1.0 times of ligand moles nickel acetate, be heated to 40 DEG C reaction 8 it is small when, reaction
Solvent is concentrated in vacuo after terminating, dichloromethane is added and separates out solid, filter and simultaneously washed with hexane, dry Raney nickel, its
Structural formula is as follows, and R is methyl.
Reacted under anhydrous and oxygen-free and inert gas shielding, first in the ampulla after being toasted with high pure nitrogen gas washing
Order adds the levorotatory lactide of the above-mentioned Raney nickels of 10 μm of ol, 10 μm of ol benzylalcohols, 8 mL toluene and 2 mmol, then puts
In 110oIn the oil bath of C, when reaction 72 is small after add a small amount of water and terminate reaction, with methanol extraction, washing for several times, vacuum at room temperature
It is dry, 0.10 gram, 34.7 % of yield is obtained, molecular weight 6.3 ten thousand.The Raney nickel is too low to the polymerization activity of lactide, without valency
Value.
Comparative example 2
The preparation of Al catalysts：Ligand structure formula such as following formula used in ligand（LH2）, reaction process is：In anhydrous and oxygen-free and inertia
Under gas shield, 0.20 g of ligand is dissolved in 10 mL toluene, the trimethyl of 1.0 times of ligand moles is added at -5 DEG C
Aluminium, be slowly increased to be heated to after room temperature 80 DEG C of reactions 12 it is small when, reaction is concentrated in vacuo solvent after terminating, and adds dry hexane and analyses
Go out solid, filter and simultaneously washed with hexane, dry Al catalysts, its structural formula LAlMe as follows.
Method according to embodiment 29 prepares polylactide, unlike：Catalyst used is the Al catalysts.In nothing
Reacted under water anaerobic and inert gas shielding, sequentially add 50 μ in the ampulla after being toasted with high pure nitrogen gas washing first
The mol Al catalysts, 50 μm of ol benzylalcohols, the rac-lactide of 10 mL toluene and 5 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 reacting 36 hours for 20 DEG C without product, illustrate that the catalyst can not be catalyzed at a lower temperature
The polymerization of lactide.
0.57 gram of product, 79.2 % of yield, molecular weight 1.3 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 29, stereoselectivity and activity are all than relatively low.
Comparative example 3
Method according to embodiment 25 prepares polylactide, unlike：Catalyst used is patent 201410609375.8
Catalyst used in middle embodiment 10.Gained polylactide is heterotactic polylactide after reaction, and quality is
0.67g, yield 93.1%, molecular weight are 1.6 ten thousand, heterotactic stereoselectivityP r For 0.71.
Comparative example 4
Under nitrogen atmosphere, 0.30 g of compound A are dissolved in 10 mL dry toluenes, 1.1 times of compound A is added at -5 DEG C and are rubbed
You amount triisobutyl aluminium, after question response temperature is raised to room temperature naturally, be heated to 110 DEG C reaction 24 it is small when, C=O double bond additions
Reaction can not carry out, and cannot be expected aluminum complex.
Comparative example 5
The preparation of Al catalysts：Under nitrogen atmosphere, 0.30 g of compound A are dissolved in 9 mL dry toluenes, are added at -5 DEG C
Three n-heptyl aluminium of 1.1 times of compound A moles, after question response temperature is raised to room temperature naturally, be heated to 90 DEG C reaction 2 it is small when,
Vacuum drains solvent after reaction terminates, and adds dry n-hexane washing, filtering, drying, obtains 0.18 g solids, yield
30.0% (yield of aluminium compound is relatively low).
Method according to embodiment 25 prepares polylactide, unlike：Catalyst used is the Al catalysts.Reaction
The quality of products obtained therefrom is 0.32g afterwards, and yield 44.4%, molecular weight is 1.2 ten thousand, isotaxy stereoselectivityP m For 0.70.
Comparative example 6
The preparation of Al catalysts：Under nitrogen atmosphere, 0.20 g of following formula: compound LD 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 90 DEG C of reactions 3
Hour, vacuum drains solvent after reaction terminates, and adds dry n-hexane washing, filtering, drying, obtains 0.21 g solids,
Structural formula such as following formula LDAlMe2, yield 85.7%, which does mass spectral characteristi and finds that such ligand can only after hydrolysis
Unilateral generation addition reaction（HRESI-MS: m/z cacld. C20H18N2O4 [M-H]-; 349.1188, found:
349.1190）.
Method according to embodiment 25 prepares polylactide, unlike：Catalyst used is the Al catalysts.Reaction
The quality of products obtained therefrom is 0.24g afterwards, and yield 33.3%, molecular weight is 0.9 ten thousand, no stereoselectivity.
Claims (9)
1. a kind of four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base, it is characterized in that：Shown in its structural formula following II；Wherein, R is
The straight chained alkyl of C1-C6, is preferably methyl, ethyl or n-hexyl；
。
A kind of 2. preparation method of the four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base described in claim 1, it is characterized in that bag
Include following steps：Compound A is added in organic solvent, -10~0 oTrialkylaluminium is added under C, makes reaction temperature after adding
Naturally it is warmed to room temperature, temperature is then risen to 30~110oC is reacted, and adds water into reaction solution after reaction, fully
Liquid separation is stood after mixing, collects organic phase obtained by liquid separation, organic solvent is recycled, obtains crude product, crude product is recrystallized, obtain
The four symmetrical ligands of tooth nitrogen oxygen containing ethylenediamine base shown in formula II；Compound A structure formula is as follows：
。
3. preparation method according to claim 2, it is characterized in that：The alkyl of the trialkylaluminium is the straight chain alkane of C1-C6
Base, is preferably methyl, ethyl or n-hexyl；The organic solvent is dry hexane, toluene and one kind in hexamethylene or two
Kind；Recrystallization solvent is methanol or/and ethanol.
4. preparation method according to claim 2, it is characterized in that：The molar ratio 1 of compound A and trialkylaluminium：1~1.3,
It is preferred that 1：1~1.05.
5. preparation method according to claim 2, it is characterized in that：Consumption of organic solvent for reaction raw materials gross mass 5~
40 times；The dosage of water is the mole of 3 times of compound A.
6. preparation method according to claim 2, it is characterized in that：It is raised to room temperature and temperature is risen to 30~110 again lateroC
（It is preferred that 40~60oC）When reaction 1~12 is small, when preferably reaction 3~6 is small.
7. preparation method according to claim 2, it is characterized in that：Reaction carries out under gas shield.
8. the four symmetrical ligand of tooth nitrogen oxygen the urging as cyclic lactone ring-opening polymerization for containing ethylenediamine base described in claim 1
The application of the ligand of agent, it is preferred that the cyclic lactone is levorotatory lactide, Study of Meso-Lactide, rac-lactide, second are handed over
Ester or caprolactone.
9. a kind of catalyst of cyclic lactone ring-opening polymerization, it is characterized in that：Its structural formula described in formula I, wherein, R is
The straight chained alkyl of C1-C6, is preferably methyl, ethyl or n-hexyl；
。
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| Title |
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| GREGORY J. HITCHINGS等: "Some Isoindolo-fused Heterocyclic Systems by Cyclodehydration of N- Arylal kyl-3- hydroxyphthal imidines", 《J. CHEM. SOC. PERKIN TRANS.》 * |
| STUART L. HANCOCK等: "Aluminium salalen complexes based on 1,2-diaminocyclohexane and their exploitation for the polymerisation of rac-lactide", 《DALTON TRANSACTIONS》 * |
| 朱葆佺: "《新编药物合成反应路线图设计与制备工艺新技术实务全书》", 31 March 2005, 天津电子出版社 * |
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