CN110156833A - N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound preparation method and application - Google Patents
N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound preparation method and application Download PDFInfo
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- CN110156833A CN110156833A CN201910484609.3A CN201910484609A CN110156833A CN 110156833 A CN110156833 A CN 110156833A CN 201910484609 A CN201910484609 A CN 201910484609A CN 110156833 A CN110156833 A CN 110156833A
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- Prior art keywords
- salicylide
- added
- diamines
- aluminium compound
- reaction
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 48
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- -1 diamines aluminium compound Chemical class 0.000 title claims abstract description 26
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229960004217 benzyl alcohol Drugs 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 6
- JUURKODRYDZDKT-UHFFFAOYSA-N benzaldehyde;diphenylphosphane Chemical compound O=CC1=CC=CC=C1.C=1C=CC=CC=1PC1=CC=CC=C1 JUURKODRYDZDKT-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 235000010210 aluminium Nutrition 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001399 aluminium compounds Chemical class 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- XDGYHAAUHYNDMA-UHFFFAOYSA-N benzyl hypochlorite Chemical compound ClOCC1=CC=CC=C1 XDGYHAAUHYNDMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical compound [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 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 2
- 239000012074 organic phase Substances 0.000 claims description 2
- ZYDGQQTXLBNSGJ-UHFFFAOYSA-N oxonan-2-one Chemical compound O=C1CCCCCCCO1 ZYDGQQTXLBNSGJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 241000219000 Populus Species 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 150000004705 aldimines Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 150000002596 lactones Chemical group 0.000 abstract description 5
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000004632 polycaprolactone Substances 0.000 description 17
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 12
- 229920001610 polycaprolactone Polymers 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 7
- 238000000710 polymer precipitation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 150000003938 benzyl alcohols Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920003232 aliphatic polyester Polymers 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 244000061458 Solanum melongena Species 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- AUNUWCUIXJHONI-UHFFFAOYSA-N C(C1=CC=CC=C1)=O.[P] Chemical compound C(C1=CC=CC=C1)=O.[P] AUNUWCUIXJHONI-UHFFFAOYSA-N 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920000229 biodegradable polyester Polymers 0.000 description 2
- 239000004622 biodegradable polyester Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004633 polyglycolic acid Substances 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- MHIIOCDXWOLLNO-UHFFFAOYSA-N propan-2-ol;zinc Chemical compound [Zn].CC(C)O MHIIOCDXWOLLNO-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
-
- 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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of application in the invention discloses N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound preparation method and its in terms of the lactone and lactide ring-opening polymerisation.The preparation of N provided by the invention, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound is convenient, low in cost, and property is stablized；Structure novel, containing multiple functions group, activity is high when ring-opening polymerization of lactone by catalysis, controllability is good, is able to suppress chain tra nsfer and chain termination, and the polyester macromolecule material molecule amount of preparation is controllable, and molecular weight distribution is low.
Description
Technical field
The present invention relates to the preparation method of a kind of organo-aluminum compound and application, in particular to N, N '-salicylides-diphenyl
The preparation method of phosphorus benzaldehyde contracting diamines aluminium compound and its application in terms of caprolactone and lactide ring-opening polymerisation.
Background technique
Degradable polyester high molecular material it is environmental-friendly, in terms of have compared to conventional polymer material
Apparent advantage is material of new generation, with broad prospects for development, and meets the requirement of ecology and sustainable development.This its
In, aliphatic polyester is a kind of very important degradable high polymer material, has obtained quick development in recent years.
Biodegradable polyesters such as PCL, PLA etc. have good biocompatibility, biological degradability, in natural environment item
Fully biodegradable under part does not generate any pollution to environment, thus is widely used in field of medicaments, such as may be used as medicine
Object carrier adjusts drug release rate by control degradation rate, also acts as operation suture thread, can be natural in vivo
Degradation, it is nontoxic to organism, without taking out stitches.In addition, biodegradable polyesters are also developing to industry, agriculture field,
It is excellent environment-friendly material to replace using petroleum as the material difficult to degrade such as the plastics of raw material.
It studies extensively at present and the aliphatic polyester of application includes polylactic acid (PLA), polycaprolactone (PCL), polyglycolic acid
(PGA), poly butyric ester (PHB) and its their copolymer, the main method preparation by catalysis monomer ring-opening polymerisation are general
There are isopropanol zinc, stannous octoate etc. all over the catalyst used.Wherein the most widely used is stannous octoate, it has faster
Reaction rate, the polyester material that available yield is high, molecular weight is high, but be not very high, need there is also reactivity
The shortcomings that wanting longer reaction time and higher reaction temperature.In recent years, organic metal aluminium compound is urged since it is outstanding
Change the characteristic in terms of lactone ring opening polymerization, is received much attention as ring-opening polymerization catalyst, be used to prepare molecular weight
Controllably, narrow molecular weight distribution, block or stereoregulated biodegradable aliphatic polyester high molecular material.These organic metal
In Al catalysts more representative catalyst model include salung (Salen) Al catalysts (J.Am.Chem.Soc.,
2002,124,1316；Proc.Natl.Acad.Sci.U.S.A.2006,103,15343), salicylic alidehyde imine Al catalysts
(Macromolecules,2005,38,5363；Dalton Trans.2012,41,11587；Organometallics 2009,
28,2179), bridging bis-phenol-Al catalysts (Macromolecules 2001,34,6196), tetraphenylporphyrin Al catalysts
(J.Am.Chem.Soc.2004,126,11030), bimetallic Al catalysts (Organometallics 2014,33,6474；
Chem.Commun.2008,4717)。
Applicant reports a series of aluminium gold metal catalysts early period, is used for aliphatic poly Lipase absobed, such as Chinese
J.Polym.Sci.2018,36,149；J.Polym.Sci.,Part A:Polym.Chem.2018,56,611；New
J.Chem.2017,41,2358；Organometallics 2017,36,1736；And related invention patent is applied for
ZL201610369322.2, ZL201610370061.6, ZL201610383016.4.Catalyst involved by above-mentioned report or patent
It is nitrogenous and oxygen aluminium gold metal catalyst, and the present invention reports the aluminium gold metal catalyst of a kind of oxygen-containing, phosphorus and nitrogen, especially relates to
And N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound preparation method and its application in ring-opening polymerisation.Institute
The Al catalysts of report have the characteristics that structure novel, prepare it is simple, at low cost, activity it is high, what is especially introduced is noncoordinating
Diphenylphosphine is able to suppress chain tra nsfer and chain termination, and polymerization controllability is good, prepared aliphatic polyester have microstructure it is controllable,
The characteristics of component is high, degradable, good biocompatibility.
Summary of the invention
The object of the present invention is to provide a kind of N, the preparations of N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound
Method and its application in ring-opening polymerisation.
The present invention provides N shown in a kind of formula (I), and N '-salicylide-diphenylphosphine benzaldehyde contracts two amine ligands and a kind of (II)
Shown N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound:
Wherein, R1, R2 are respectively selected from hydrogen, methyl, tert-butyl, phenyl, nitro, fluorine, chlorine and bromine.X be selected from methyl, ethyl,
Isopropyl, benzyl, methoxyl group, benzyloxy, chlorine.
Preferably, aluminum complex of the present invention is selected from any one following complex:
Al1:L1AlMe2L1=2-OH-3,5-tBu-C6H2-CH2-NH-C6H4- N=CH-C6H4-2-PPh2；
Al2:L2AlMe2L2=2-OH-3,5-H-C6H2-CH2-NH-C6H4- N=CH-C6H4-2-PPh2；
Al3:L3AlMe2L3=2-OH-3-Ph-5-H-C6H2-CH2-NH-C6H4- N=CH-C6H4-2-PPh2；
The present invention provides N, N '-salicylide-diphenylphosphine benzaldehyde two amine ligands of contracting preparation methods comprising following
Step:
After o-phenylenediamine is mixed with the first salicylide or substituted salicylic aldehydes by 2~5:1 molar ratio, catalytic amount is added
P-methyl benzenesulfonic acid (5mg~20mg), reacted 10~18 hours in alcohol.Reaction solution is concentrated under reduced pressure, is obtained by filtration to obtain
Single salicylaldehyde imine intermediate.Above-mentioned intermediate is dissolved in methanol, the sodium borohydride of 4-8 molar equivalent, room temperature reaction 10 is added
~18 hours, reaction solution revolving is removed, obtained solid water and methylene chloride extraction, last organic phase uses alcohol after being spin-dried for
Solvent carries out being recrystallized to give salicylide amine intermediate.Salicylide amine intermediate is dissolved into alcohol solvent, 1 mole is added and works as
The diphenylphosphine benzaldehyde of amount, and the p-methyl benzenesulfonic acid (5mg~20mg) of catalytic amount is added, it reacts 10-18 hours.It will be anti-
It answers liquid to be concentrated under reduced pressure, is obtained by filtration to obtain N, N '-salicylide-diphenylphosphine benzaldehyde two amine ligands of contracting.
The present invention provides N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium alkyl aluminum compound preparation method,
Itself the following steps are included:
By N, N '-salicylide-diphenylphosphine benzaldehyde two amine ligands of contracting are dissolved in 30-100mL anhydrous solvent, are added 1.0
~1.5 equivalent trimethyl aluminiums are stirred at room temperature 12~24 hours under nitrogen protection, solvent are removed under reduced pressure, washs three with poor solvent
It is secondary, obtain corresponding aluminium compound.
In above-mentioned preparation method, the anhydrous solvent is selected from benzene,toluene,xylene, tetrahydrofuran, methylene chloride；It is bad
Solvent is selected from n-hexane, pentane, normal heptane, hexamethylene.
The present invention also provides N shown in above-mentioned formula (II), N '-salicylides-diphenylphosphine benzaldehyde contracting diamines aluminium compound
Application in catalyzing lactone and lactide ring-opening polymerization.
In above-mentioned application, the lactone and lactide include lactide, glycolide, butyrolactone, valerolactone, caprolactone, in heptan
Ester, caprylolactone.
In above-mentioned application, the N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound and the lactide and interior
The molar ratio of ester is 1:(50~10000).
In above-mentioned application, the solvent of the polymerization reaction can be benzene, toluene, n-hexane, tetrahydrofuran and methylene chloride.
In above-mentioned application, the temperature of the polymerization reaction is 0 DEG C~110 DEG C.
In above-mentioned application, the time of the polymerization reaction is 0.1~72 hour.
In above-mentioned application, alcohol can be added as initiator in the polymerization reaction, the alcohol be methanol, ethyl alcohol, isopropanol,
N-butanol, ethylene glycol, glycerine, benzylalcohol；The alcohol and the N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines calorize are closed
The molar ratio of object is 0.1~50:1.
N provided by the invention, N '-salicylide-most important feature of diphenylphosphine benzaldehyde contracting diamines aluminium compound are them
Polymerization reaction center it is active polymerization and stereoselectivity polymerization feature, feature first is that molecular weight of product with monomer
Increase and approximately linear increase, feature second is that for having chiral monomer to obtain isotachyte.
N provided by the invention, N '-salicylide-structure novel of diphenylphosphine benzaldehyde contracting diamines aluminium compound, preparation side
Just, low in cost, property is stablized, while catalytic activity with higher and stereoselective, be particularly suitable for catalysis caprolactone and
Lactide ring-opening polymerisation.By the control to polymeric reaction condition, the molecular size range of polymer can be regulated and controled, from thousands of to several
100000.
Detailed description of the invention
Fig. 1 is the crystal structure figure of compound Al1.
Fig. 2 is that the GPC of 3 resulting polymers of embodiment schemes.
Specific embodiment
The present invention is further illustrated by embodiment, but the present invention is not limited thereto.The embodiment of the present invention can make this
The present invention is more completely understood in technical professional.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1, N, N '-salicylide -1 (2-OH-3,5-tBu-C of diphenylphosphine benzaldehyde contracting diamines ligand L6H2-CH2-
NH-C6H4- N=CH-C6H4-2-PPh2) preparation
O-phenylenediamine 21.6g (200mmol) is dissolved into 500mL ethyl alcohol, bis- uncle of 23.4g (100mmol) 3,5- is weighed
Butyl salicylide, 10mg p-methyl benzenesulfonic acid are added in reaction system, 80 DEG C of reaction 12h.Contact plate measures after the reaction was completed, will be anti-
Bottle is answered to take out from oil bath, spontaneous recovery to room temperature.Partial solvent is removed by revolving, there should be solid precipitation in the process, will consolidate
Body filters out, and is washed with ethyl alcohol, and filtrate is put into refrigerator recrystallization, and the solid that this two parts obtains drains shared 27.3g intermediate
3,5-tBu-2-(OH)C6H2CH=N-C6H4-NH2.By (the 3,5- of above-mentioned synthesistBu-2-(OH)C6H2CH=N-C6H4-NH2)
6.49g (20mmol) dissolves in 200mL methanol, obtains orange clear solution.3.0g sodium borohydride solids are weighed, several times slowly
Ground is added in reaction flask, is during which had a large amount of bubble and is emerged, and is reacted one day at room temperature.Contact plate measures after reaction, will
Solvent is removed using revolving, and water is added into reaction flask and methylene chloride is extracted, then with the multiple extraction water of methylene chloride
Methylene chloride is mutually collected into together by phase until not developing the color when water phase contact plate, and anhydrous magnesium sulfate is added and removes in methylene chloride phase
Water.Filtrate is spin-dried for except clean rear filtering, obtains grease by water.Crude product recrystallizing methanol obtains intermediate 3,5-tBu-2-(OH)C6H2-CH2-NH-C6H4-NH25.0g(15.3mmol).Weigh 3.92g (12mmol) intermediate 3,5-tBu-2-
(OH)C6H2-CH2-NH-C6H4-NH2It is added in the round-bottomed flask of 500mL, 200mL ethyl alcohol is added and is dissolved.Weigh 3.8g
(13.2mmol) 2- diphenylphosphine benzaldehyde and 10mg p-methyl benzenesulfonic acid are added in system, obtain yellow turbid, then to circle
Methylene chloride is added dropwise in the flask of bottom, until all dissolutions of 2- diphenylphosphine benzaldehyde, reacts 1 day at room temperature, with reaction
Progress, there is a large amount of yellow solid to separate out from solution.After reaction by contact plate measurement, yellow is consolidated by filtering
Body is separated with solvent, filtrate to about 50mL, is put into refrigerator and is recrystallized by concentrated by rotary evaporation, after one day by recrystallization to consolidate
Body filters out, and is put into eggplant shaped reaction bottle and drains with the yellow solid filtered out before, shares N, N '-salicylide-diphenyl
Two amine ligand 5.8g (9.69mmol) of phosphorus benzaldehyde contracting.1H NMR(400MHz,CDCl3): δ 9.01 (d, 1H, J=4.5Hz, CH=
N), 8.80 (s, 1H, OH), 8.05 (m, 1H, ArH), 7.43 (t, 1H, J=14.8Hz, ArH), 7.33-7.30 (m, 7H, ArH),
7.26-7.22 (m, 4H, ArH), 7.12-7.08 (m, 1H, ArH), 7.01 (d, 1H, J=2.2Hz, ArH), 6.94-6.88 (m,
2H, ArH), 6.82-6.77 (m, 2H, ArH), 5.27 (br, 1H, C-NH), 4.33 (d, 2H, J=5.1Hz, CH2-N),1.41
(d,9H,CMe3),1.30(d,9H,CMe3).13C NMR(CDCl3,400MHz):δ157.83,157.67,153.80,143.11,
141.22,139.50,139.29,139.13,138.49,138.28,137.09,136.99,136.16,134.09,134.02,
133.89,130.79,129.93,129.89,128.88,128.67,128.60,127.81,123.31,123.22,122.67,
120.19,117.14,114.52,50.26,34.98,34.26,31.72,29.74.31P NMR(CDCl3,400MHz):δ-
10.07.
Embodiment 2, compound Al1 (L1AlMe2) preparation
Weigh the 1 [2-OH-3,5-tBu-C of ligand L of the preparation of 1.20g (2mmol) embodiment 16H2-CH2-NH-C6H4- N=
CH-C6H4-2-PPh2] be added in the eggplant shaped reaction bottle of 100mL, vacuum and exchange nitrogen 5 times, the air in reaction flask is all set
It is changed to nitrogen.20mL anhydrous methylene chloride is injected into reaction flask under conditions of nitrogen protection with syringe, is obtained faint yellow
Reaction flask is put into the cryostat of isopropanol and liquid nitrogen by clear solution.The trimethyl aluminium of 1.1mL (2.2mmol) is taken with syringe
(toluene solution that concentration is 2M), injects in reaction flask in the case where nitrogen protection.After trimethyl aluminium adds, cryostat is not removed
It walks, is slowly restored to room temperature, be stirred to react 2 hours.After reaction, cold-trap is taken out by solvent concentration to 3-5mL, then in nitrogen
The anhydrous n-hexane that about 20mL is injected under atmosphere, reaction flask is sealed after adding, and is put into refrigerator and is recrystallized, two days later
There is a large amount of solid to be precipitated.The eggplant shaped reaction bottle for preparing what a 50mL, is dried in an oven, and cool, pumping is taken out with vacuum pump
Vacuum is changed nitrogen 5 times, is nitrogen by the air displacement in bottle.The reaction flask of recrystallization is taken out from refrigerator, with being tied with filter paper
Long single needle is filtered in the environment of nitrogen protection, and solid is drained with vacuum pump, and weight 1.10g is weighed in glove box
(1.76mmol), yield 88%.1H NMR(CDCl3, 400MHz): δ 8.91 (d, 1H, J=3.9Hz, N=CH), 7.92-7.90
(m, 1H, ArH), 7.44-7.40 (t, 1H, J=15.7Hz, C-NH), 7.32-7.08 (m, 17H, ArH), 6.92-6.86 (m,
3H, ArH), 4.74-4.68 (t, 1H, J=22.5Hz, N-CH2), 4.00 (d, 1H, J=11.9Hz, N-CH2),1.48(s,9H,
CMe3),1.12(s,9H,CMe3),-0.92(s,3H,Al-CH3),-1.03(s,3H,Al-CH3).13C NMR(CDCl3,
400MHz):δ 160.43,160.31,156.80,142.27,138.54,138.27,136.98,134.98,134.36,
133.35,133.16,131.51,128.97,128.77,128.60,127.48,126.61,124.80,124.16,121.85,
121.57,117.57,54.36,35.16,34.08,31.71,29.94,-10.26,-11.08.31P NMR(CDCl3,
400MHz):δ-10.53.
The polymerization of embodiment 3, compound Al1 and benzylalcohol catalysis 6-caprolactone
In Schlenk bottles, under the conditions of anhydrous and oxygen-free, 0.228g 6-caprolactone is added, 1mL toluene, 20 μm of ol cooperations are added
Object Al1,2.1 μ L benzylalcohols (20 μm of ol) are dissolved in 1mL toluene, are added in Schlenk bottles with syringe and cause polymerization.Control reaction
5% acetic acid methanol solution of 1mL is added in 20 DEG C of reaction 6h in temperature, and pouring into methanol makes polymer Precipitation, true after filtering
Obtain polycaprolactone within sky dry 24 hours.Conversion ratio: 93%.The number-average molecular weight M of the polycaprolactonen:1.24×104G/mol, point
Son amount distribution PDI=1.14.The measuring method of number-average molecular weight be gel permeation chromatography, Agilent 1260Infinity,
THF is solvent, flow velocity 1mL min-1, 40 DEG C of test temperature.
The polymerization of embodiment 4, compound Al1 and benzylalcohol catalysis 6-caprolactone
In Schlenk bottles, under the conditions of anhydrous and oxygen-free, 0.228g 6-caprolactone is added, 1mL TOL, 20 μm of ol cooperations are added
Object Al1,2.1 μ L benzylalcohols (20 μm of ol) are dissolved in 1mL TOL, are added in Schlenk bottles with syringe and cause polymerization.Control reaction
5% acetic acid methanol solution of 1mL is added in 70 DEG C of reaction 2h in temperature, and pouring into methanol makes polymer Precipitation, true after filtering
Obtain polycaprolactone within sky dry 24 hours.Conversion ratio: > 99%.The number-average molecular weight M of the polycaprolactonen:1.31×104G/mol,
Molecular weight distribution PDI=1.13.The measuring method of number-average molecular weight is gel permeation chromatography, Agilent
1260Infinity, THF are solvent, flow velocity 1mL min-1, 40 DEG C of test temperature.
The polymerization of embodiment 5, compound Al1 and benzylalcohol catalysis 6-caprolactone
In Schlenk bottles, under the conditions of anhydrous and oxygen-free, 0.228g 6-caprolactone is added, 1mL TOL, 20 μm of ol cooperations are added
Object Al1,2.1 μ L benzylalcohols (20 μm of ol) are dissolved in 1mL TOL, are added in Schlenk bottles with syringe and cause polymerization.Control reaction
5% acetic acid methanol solution of 1mL is added in 110 DEG C of reaction 20min in temperature, and pouring into methanol makes polymer Precipitation, filtering
It is dried in vacuo 24 hours to obtain polycaprolactone afterwards.Conversion ratio: 96%.The number-average molecular weight M of the polycaprolactonen:1.23×104g/
Mol, molecular weight distribution PDI=1.18.The measuring method of number-average molecular weight is gel permeation chromatography, Agilent
1260Infinity, THF are solvent, flow velocity 1mL min-1, 40 DEG C of test temperature.
The polymerization of embodiment 6, compound Al1 and benzylalcohol catalysis 6-caprolactone
In Schlenk bottles, under the conditions of anhydrous and oxygen-free, 0.228g 6-caprolactone is added, 1mL TOL, 10 μm of ol cooperations are added
Object Al1,1.1 μ L benzylalcohols (10 μm of ol) are dissolved in 1mL TOL, are added in Schlenk bottles with syringe and cause polymerization.Control reaction
5% acetic acid methanol solution of 1mL is added in 110 DEG C of reaction 20min in temperature, and pouring into methanol makes polymer Precipitation, filtering
It is dried in vacuo 24 hours to obtain polycaprolactone afterwards.Conversion ratio: 96%.The number-average molecular weight M of the polycaprolactonen:2.61×104g/
Mol, molecular weight distribution PDI=1.22.The measuring method of number-average molecular weight is gel permeation chromatography, Agilent
1260Infinity, THF are solvent, flow velocity 1mL min-1, 40 DEG C of test temperature.
The polymerization of embodiment 7, compound Al1 and benzylalcohol catalysis 6-caprolactone
In Schlenk bottles, under the conditions of anhydrous and oxygen-free, 0.228g 6-caprolactone is added, 1mL TOL, 4 μm of ol complexs are added
Al1,0.4 μ L benzylalcohol (4 μm of ol) are dissolved in 1mL TOL, are added in Schlenk bottles with syringe and cause polymerization.Control reaction temperature
In 110 DEG C of reaction 30min 5% acetic acid methanol solution of 1mL is added, pouring into methanol makes polymer Precipitation, after filtering in degree
Obtain polycaprolactone within vacuum drying 24 hours.Conversion ratio: > 99%.The number-average molecular weight M of the polycaprolactonen:5.12×104g/
Mol, molecular weight distribution PDI=1.21.The measuring method of number-average molecular weight is gel permeation chromatography, Agilent
1260Infinity, THF are solvent, flow velocity 1mL min-1, 40 DEG C of test temperature.
The polymerization of embodiment 8, compound Al1 and benzylalcohol catalysis 6-caprolactone
In Schlenk bottles, under the conditions of anhydrous and oxygen-free, 0.228g 6-caprolactone is added, 1mL TOL, 1 μm of ol complex is added
Al1,0.1 μ L benzylalcohol (1 μm of ol) are dissolved in 1mL TOL, are added in Schlenk bottles with syringe and cause polymerization.Control reaction temperature
In 110 DEG C of reaction 30min 5% acetic acid methanol solution of 1mL is added, pouring into methanol makes polymer Precipitation, after filtering in degree
Obtain polycaprolactone within vacuum drying 24 hours.Conversion ratio: > 99%.The number-average molecular weight M of the polycaprolactonen:21.1×104g/
Mol, molecular weight distribution PDI=1.25.The measuring method of number-average molecular weight is gel permeation chromatography, Agilent
1260Infinity, THF are solvent, flow velocity 1mL min-1, 40 DEG C of test temperature.
The polymerization of embodiment 9, compound Al1 and benzylalcohol catalysis L- lactide
In Schlenk bottles, under the conditions of anhydrous and oxygen-free, 0.288g L- lactide is added, 1mL TOL, 20 μm of ol cooperations are added
Object Al1,2.1 μ L benzylalcohols (20 μm of ol) are dissolved in 1mL TOL, are added in Schlenk bottles with syringe and cause polymerization.Control reaction
5% acetic acid methanol solution of 1mL is added in 110 DEG C of reaction 2h in temperature, and pouring into methanol makes polymer Precipitation, true after filtering
Obtain polycaprolactone within sky dry 24 hours.Conversion ratio: 91%, steric regularity 98%.The number-average molecular weight M of the polycaprolactonen:
1.17×104G/mol, molecular weight distribution PDI=1.16.The measuring method of number-average molecular weight is gel permeation chromatography,
Agilent 1260Infinity, THF are solvent, flow velocity 1mL min-1, 40 DEG C of test temperature.
Claims (9)
- Two amine ligands 1. one kind N, N '-salicylide-diphenylphosphine benzaldehyde contract, shown in structure such as formula (I):Wherein, R1, R2 are respectively selected from hydrogen, methyl, tert-butyl, phenyl, nitro, fluorine, chlorine and bromine；X is selected from methyl, ethyl, isopropyl Base, benzyl, methoxyl group, benzyloxy, chlorine.
- The preparation method of two amine ligands 2. N according to claim 1, N '-salicylide-diphenylphosphine benzaldehyde contract, step It is as follows: after o-phenylenediamine is mixed with the first salicylide or substituted salicylic aldehydes by 2~5:1 molar ratio, catalytic amount is added P-methyl benzenesulfonic acid 5mg~20mg reacts 10~18 hours in alcohol；Reaction solution is concentrated under reduced pressure, is obtained by filtration to obtain single water Poplar aldimine intermediate；Above-mentioned intermediate is dissolved in methanol, the sodium borohydride of 4-8 molar equivalent, room temperature reaction 10~18 is added Hour, reaction solution revolving is removed, obtained solid water and methylene chloride extraction, last organic phase uses alcoholic solvent after being spin-dried for It carries out being recrystallized to give salicylide amine intermediate；Salicylide amine intermediate is dissolved into alcohol solvent, 1 molar equivalent is added Diphenylphosphine benzaldehyde, and p-methyl benzenesulfonic acid 5mg~20mg of catalytic amount is added, it reacts 10-18 hours；Reaction solution is subtracted Pressure concentration is obtained by filtration to obtain N, N '-salicylide-diphenylphosphine benzaldehyde two amine ligands of contracting.
- 3. one kind N, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound, shown in structure such as formula (II):Wherein, R1, R2 are respectively selected from hydrogen, methyl, tert-butyl, phenyl, nitro, fluorine, chlorine and bromine；X is selected from methyl, ethyl, isopropyl Base, benzyl, methoxyl group, benzyloxy, chlorine.
- 4. N according to claim 3, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound preparation method, Steps are as follows: by N, N '-salicylide-diphenylphosphine benzaldehyde two amine ligands of contracting are dissolved in 30-100mL anhydrous solvent, are added 1.0 ~1.5 equivalent trimethyl aluminiums are stirred at room temperature 12~24 hours under nitrogen protection, solvent are removed under reduced pressure, washs three with poor solvent It is secondary, obtain corresponding aluminium compound.
- 5. according to the method described in claim 4, anhydrous solvent used in reaction is derived from benzene,toluene,xylene, tetrahydrofuran； Poor solvent is selected from n-hexane, pentane, normal heptane, hexamethylene；Range of reaction temperature is 20~100 DEG C；Reaction time is 12 ~24 hours.
- 6. the application of N as claimed in claim 3, N '-salicylide-diphenylphosphine benzaldehyde contracting diamines aluminium compound, feature exist In for being catalyzed the polymerization of caprolactone, lactide, glycolide, butyrolactone, valerolactone, heptalactone, caprylolactone etc..
- 7. application according to claim 7, which is characterized in that with N as claimed in claim 3, N '-salicylide-diphenyl Phosphorus benzaldehyde contracting diamines aluminium compound is catalyst, and catalyst structure is novel, and catalyst activity is high, controllability is good, can 0~ 110 DEG C, it is catalyzed caprolactone polymerization, the molar ratio of catalyst and caprolactone is 1:50~10000 when polymerization；Polymerization time 0.1~ 72h；Polymer solvent is selected from benzene, toluene, n-hexane, tetrahydrofuran and methylene chloride.
- 8. application according to claim 6, which is characterized in that methanol, ethyl alcohol, isopropanol, just can be added when causing polymerization Butanol, ethylene glycol, glycerine, benzylalcohol are as initiator, initiator and catalyst n, N '-salicylide-diphenylphosphine benzaldehyde contracting The molar ratio of diamines aluminium compound is 0.1~50:1.
- 9. application according to claim 6, which is characterized in that prepared polymer molecular weight it is controllable (0.50-30.0 × 104G/mol), molecular weight distribution is low (1.05-1.25).
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| CN109705159A (en) * | 2019-01-30 | 2019-05-03 | 青岛科技大学 | A kind of preparation method and application of phosphorous nitrogen ligand alkyl aluminum compound |
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| CN106831843A (en) * | 2017-01-19 | 2017-06-13 | 青岛科技大学 | The preparation method of double (salicylide) the contracting o-phenylenediamine aluminium compounds of asymmetric N, N ' and application |
| CN109705159A (en) * | 2019-01-30 | 2019-05-03 | 青岛科技大学 | A kind of preparation method and application of phosphorous nitrogen ligand alkyl aluminum compound |
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