CN104211724A - Beta-diketiminate alkoxyl aluminum hydride compound, synthesis method and applications thereof - Google Patents
Beta-diketiminate alkoxyl aluminum hydride compound, synthesis method and applications thereof Download PDFInfo
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Abstract
The invention relates to a beta-diketiminate alkoxyl aluminum hydride compound, a synthesis method and applications thereof. The compound is prepared by alcoholysis reactions of beta-diketiminate aluminum hydride. The aluminoxane complex can be used as an active catalyst for ring-opening polymerization of epsilon-caprolactone, and has the characteristics of quick reaction speed and controllable molecular weight of the reaction product. The molecular weight distribution of epsilon-caprolactone obtained at a high temperature can still be controlled in a narrow range.
Description
Technical field:
The present invention relates to a class beta-diketon imido grpup alkoxyl group aluminum hydride compound and its synthetic method and application, this compounds is obtained by the alcoholysis reaction of beta-diketon imido grpup aluminum hydride.This type of aikyiaiurnirsoxan beta title complex can be used as the catalyzer of the active ring-opening polymerization of 6-caprolactone, have speed of response fast, the feature that molecular weight is controlled, and the molecular weight distribution of the poly-epsilon-caprolactone obtained at relatively high temperatures still can be controlled in narrower scope.
Background technology:
Polycaprolactone is biodegradable macromolecular material, because it is biodegradable, biocompatibility, water-permeable, and the new high-tech materials such as the carrier can be used for preparing biodegradable surgical suture line, delaying controlled release medicine.Structure can be obtained for [-CH by 6-caprolactone ring-opening polymerization
2-(CH
2)
4-COO-]
npolycaprolactone, belong to thermoplastic synthetic resin.The polycaprolactone that molecular weight is higher is colorless crystalline solid; Second-order transition temperature-60 DEG C, melt temperature 63 DEG C, 250 DEG C start to decompose.Synthesize the ring-opening polymerization (ROP) that the main polymerization process of these polymkeric substance is lactone, Main Function mechanism is that living polymerization is inserted in coordination.
Once the title complex of report titanium, lanthanum, magnesium, zinc was had to be catalyzer (lnorg Chem, 2006,45 (5): 2282-2287 of causing lactone ring opening polymerization; Lnorg Chem, 2005,44 (14): 5133-5140; J Mol Catal A:Chem, 2005,240:91-98), but because of the application of its special biological medicine, catalyzer also will consider nontoxicity.Metallic aluminium has stronger lewis acidity, hypotoxicity and good biocompatibility, and the relatively front several metal complexes of its title complex advantageously.
Summary of the invention:
The object of the present invention is to provide a class containing compound of the beta-diketon imines aluminium of alkoxyl group and preparation method thereof, the present invention also aims to provide the application of such aluminum complex in 6-caprolactone ring-opening polymerization.
Novel Ligands I of the present invention, shown in the following I of its general structure:
In general formula I, Ar is the phenyl of phenyl or replacement; R is alkyl, such as methyl or ethyl or sec.-propyl or the tertiary butyl or benzyl.
1. in order to contribute to the structure more clearly understanding above-claimed cpd, illustrate below, it is emphasized that the present invention does not limit the compound of these structures following:
Ar=2,6-diisopropyl phenyl
The synthetic method of beta-diketon imido grpup alkoxyl group aluminum hydride compound, it is characterized by the compound with general formula I according to claim 1 is that compound by having following general structure II obtains through alcoholysis reaction.In general formula I I, substituent A r is specially 2,6-diisopropyl phenyl.Concrete synthetic method: under nitrogen protection;-78 DEG C ~ 100 DEG C conditions; preferably under 10 DEG C of-30 DEG C of conditions; to in the benzene of beta-diketon imido grpup aluminum hydride compound II or toluene or hexane solution; drip the alcohol of same molar, after being added dropwise to complete, remove a small amount of insoluble impurity after filtration; filtrate removes volatile matter under vacuum condition, and residuum is had the beta-diketon imido grpup alkoxyl group aluminum hydride compound of general structure I more as claimed in claim 1 with dry normal hexane recrystallization.
Reaction formula is as follows:
Ar is 2.6-diisopropyl phenyl
Alkoxyl group R as previously mentioned;
Described organic solvent is normal hexane or toluene or benzene etc.;
When preparing compound described in general formula I, the mol ratio of Compound II per and alcohol is 1: 1;
The aluminum alkoxide title complex of the present invention's synthesis can be used as catalyzer, for the ring-opening polymerization of catalysis 6-caprolactone.Such as in toluene, tetrahydrofuran (THF), dichloromethane solution, with the ring-opening polymerization of catalysis caprolactone under 15 ~ 110 DEG C of conditions.
All kinds of SOLVENTS used in the preparation process of aluminum alkoxide title complex of the present invention all needs the strict deoxygenation process that dewaters, and all operations all carries out under the condition of strict anhydrous and oxygen-free, illustrates no longer in addition in an experiment.
1991, Ph.Teyssie seminar have studied the research proposing aluminium isopropoxide catalysis caprolactone first, open the gate of aluminum alkoxide for the ring-opening polymerization of catalysis caprolactone, they find when temperature is 70 DEG C, aluminum isopropoxide has good catalytic activity, when monomer and catalytic proportions are about 500, needs the transformation efficiency reacting 72h caprolactone to reach 100% (Macromolecules, 1991,24 (11): 3027-3034).
Numerous seminar have studied multiple tooth aluminum compound and studies for the ring-opening polymerization of caprolactone afterwards, such as Jun Okuda seminar in 1997 have studied alkyl bridge Schiff bases alkylaluminium cpd, during polymerization caprolactone, the ratio of monomer and catalysis is 50, the molecular weight that reaction 20h obtains polymkeric substance only has 2700, catalytic activity bad (J Organomet Chem, 1997,540 (1-2): the 189-192 of compound.
Within 2002, Jui-Hsien Huang seminar synthesizes the β-one aminoalkyl aluminum compound of a series of different substituents, and attempt being used for caprolactone ring-opening polymerization research, their monomer used is 300 with catalyst concn ratio, reaction 3.5h, temperature 60 C, monomer conversion is about 90%, and the polymericular weight obtained is higher 10
5above, but molecular weight distribution is between 1.75-2.35.Within 2005, Evamarie Hey-Hawkins seminar synthesizes a series of O-Phenylene Diamine base alkylaluminium cpd, find in the research of catalysis caprolactone, when monomer and catalyst concn are 200 at that time, reaction 1h, monomer conversion is 100%, catalytic activity is higher, but the molecular weight distribution obtained is 2.79.The compound for catalysis activity of this Liang Ge seminar research is higher, but the molecular weight distribution of the polymkeric substance obtained is wider, controllability not high (lnorg Chem, 2002,41 (24): 6450-6455 of polymerization; J Mol Catal A:Chem, 2005,240:91-98).
Within 2008, Ma Haiyan seminar have studied the ring-opening polymerization of beta-diketon imido grpup alkylaluminium cpd for caprolactone, all add a small amount of alcohol in their experiment and carry out initiation ring-opening reaction, the ratio of monomer used and catalyzer is 100, temperature of reaction is 80 DEG C, what the reaction times was the shortest is 7 hours, obtain monomer conversion between 10%-90%, and the molecular weight distribution of polymkeric substance is also wider, between 1.66-3.74, because the amount adding alcohol does not wait so the amount of the aluminum alkoxide produced is also uncertain, the molecular weight of the polymkeric substance finally obtained just can not well control.The aluminium triethyl compound of Donald J.Darensbourg seminar synthesis Schiff's base four-coordination in 2011, for caprolactone ring-opening polymerization, temperature of reaction is 70 DEG C, monomer and catalytic proportions are 50, reaction 15h, and monomer conversion reaches 99%, the molecular weight of resulting polymers is 1.75, the catalytic activity of compound is not molecular weight distribution yet wider (Dalton Trans, 2008, (25): 3345-3357 of comparatively looking in the reaction times of very high needs; Dalton Trans, 2008, (25): 3345-3357).
Our compou nd synthesis method is quick, simple, experiment condition is gentle, and by product is that hydrogen is easy to removing.The compound about aluminium of summing up with top is to compared with the research of caprolactone ring-opening polymerization, our compound has higher catalytic activity and is polymerized controllability preferably, such as compound 2a, 100 DEG C time, monomer is 500 with catalyst concn ratio, reaction 1.5h, monomer conversion can reach 61%, and the molecular weight distribution of polymkeric substance is 1.30.
Embodiment:
To contribute to understanding the present invention further by following embodiment, but the present invention is not limited to this.
Embodiment 1:
The synthesis of title complex 2a:
In the schlenk bottle of 50ml, add aluminium hydrogen part (2.68g, 6.00mmo1) in glove box, add 20ml in dry toluene, add absolute methyl alcohol (0.65g, 20.20mmo1) under room temperature, have a large amount of bubble to produce, stirring at room temperature 12h, obtains slight haze solution.Drain solvent, add 30ml normal hexane, dissolve, filter muddiness, filtrate-20 DEG C of ice crystals, obtain clear crystal, filtration is drained, and obtains the heavy 1.63g of clear crystal, productive rate 57%.Fusing point: 151-153 DEG C.
1H?NMR(400MHz，298K，CDCl
3)：δ(ppm)1.07(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.13(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.18(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.22(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.71(s，6H，CCH
3)，3.06(sept，2H，2CH(CH
3)
2)，3.16(s，3H，OCH
3)，3.26(sept，2H，2CH(CH
3)
2)，5.09(s，1H，γ-CH)，7.11-7.21(m，6H，aryl-H).
13C?NMR(100MHz，298K，CDCl
3)：δ(ppm)23.3，24.5，24.6，24.9，25.1，28.0，28.4，51.3，97.2，124.1124.32，126.9，139.4，143.7，145.2，170.0。
Embodiment 2:
The synthesis of title complex 2b:
In the schlenk bottle of 50ml, add aluminium hydrogen part (2.68g, 6.00mmo1) in glove box, add the toluene of 20ml drying, add absolute ethanol (0.28g, 6.00mmo1) under room temperature, have a large amount of bubble to produce, stirring at room temperature 16h, obtains slight haze solution.Drain solvent, add 30ml normal hexane, dissolve, filter muddiness, filtrate-20 DEG C of ice crystals, obtain clear crystal, filter to drain to obtain clear crystal 2.34g, and productive rate is 80%.Fusing point: 152-153 DEG C.
1H?NMR(400MHz，293K，C
6D
6)：δ(ppm)0.47(t，
3J
H-H＝6.8Hz，3H，OCH
2CH
3)，1.08(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.13(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.18(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.21(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.70(s，6H，CCH
3)，3.08-3.25(m，4H，CH(CH
3)
2)，3.08-3.25(m，3H，OCH
2CH
3)，5.03(s，1H，γ-CH)，7.10-7.19(m，6H，aryl-H).
13C?NMR(100MHz，293K，CDCl
3)：δ(ppm)20.1，23.2，24.4，24.5，24.6，25.5，28.0，28.2，57.8，96.5，124.0，124.0，126.8，139.3，144.0，144.8，169.9。
Embodiment 3:
The synthesis of title complex 2c:
In the schlenk bottle of 50ml, add aluminium hydrogen part (2.68g, 6.00mmo1) in glove box, add the toluene of 20ml drying, add anhydrous isopropyl alcohol (0.36g, 6.00mmo1) at-78 DEG C, have bubble to produce, after reaction 3.5h, slowly rise to stirring at room temperature 12h.Drain solvent, add 20ml normal hexane, dissolve ,-20 DEG C of refrigerator crystallizations, obtain clear crystal.Filtration is drained, and obtains clear crystal 1.79g, and productive rate is 59%.Fusing point: 174-176 DEG C.
1H?NMR(400MHz，298K，CDCl
3)：δ(ppm)0.32(d，
3J
H-H＝6.0Hz，6H，OCH(CH
3)
2)，1.05(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.16(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.18(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.23(d，
3J
H-H＝6.4Hz，6H，CH(CH
3)
2)，1.72(s，6H，CCH
3)，3.14(m，
3J
H-H＝6.8Hz，4H，CH(CH
3)
2)，3.47(m，
3J
H-H＝6.0Hz，1H，OCH(CH
3)
2)，5.00(s，1H，γ-CH)，7.10～7.185(m，6H，aryl-H).
13C?NMR(100MHz，293K，CDCl
3)：δ(ppm)22.1，23.1，23.5，24.7，25.9，26.8，27.4，62.2，94.9，122.8，122.9，125.5，138.2，143.1，143.4，168.7。
Embodiment 4:
The synthesis of title complex 2d:
In the schlenk bottle of 50ml, add aluminium hydrogen part (2.68g, 6.00mmol) in glove box, add the toluene of 30ml drying, add anhydrous benzylalcohol (0.65g, 6.00mmol) under room temperature, have bubble to produce, stirring at room temperature 16h.Drain solvent, add 20ml normal hexane, dissolve ,-20 DEG C of refrigerator crystallizations, obtain clear crystal.Filtration is drained, and obtains clear crystal 1.95g, and productive rate is 80%, fusing point: 113-115 DEG C.
1H?NMR(400MHz，298K，CDCl
3)：δ(ppm)1.06(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.09(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.11(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.15(d，
3J
H-H＝6.4Hz，6H，CH(CH
3)
2)，1.73(s，6H，2CCH
3)，3.15(sept，4H，4CH(CH
3)
2)，4.23(s，2H，OCH
3Ph)，5.06(s，1H，r-CH)，6.44-7.25(m，11H，aryl-H).
13C?NMR(100MHz，293K，CDCl
3)：δ(ppm)23.1，24.2，24.5，24.6，25.6，28.0，28.4，64.1，96.4，124.2，124.21，125.4，126.9，127.4，139.1，144.2，144.6，170.1。
Embodiment 5:
The synthesis of title complex 2e:
In the schlenk bottle of 50ml, add aluminium hydrogen part (2.68g, 6.00mmol) in glove box, add the toluene of 20ml drying, under-room temperature, add anhydrous tertiary butanol (0.45g, 6.00mmol), have bubble to produce, stirring at room temperature 12h.Drain solvent, add 20ml normal hexane, dissolve ,-20 DEG C of refrigerator crystallizations, obtain clear crystal, filtration is drained, and obtains clear crystal 2.55g, and productive rate is 73%.Fusing point: 165-167 DEG C.
1H?NMR(400MHz，298K，CDCl
3)：δ(ppm)0.49(s，9H，OC(CH
3)
3)，1.02(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.15(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.19(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.26(d，
3J
H-H＝6.8Hz，6H，CH(CH
3)
2)，1.71(s，6H，CCH
3)，3.16sept，
3J
H-H＝6.8Hz，4H，CH(CH
3)
2)，5.00(s，1H，γ-CH)，7.07-7.19(m，6H，aryl-H).
13C?NMR(100MHz，293K，CDCl
3)：δ(ppm)23.2，24.0，24.4，24.7，25.6，27.8，28.3，33.0，67.7，95.8，123.6，124.0，126.5，139.7，144.6，144.2，169.7。
Embodiment 6:
Title complex 2a, 2c, 2d catalytic performance is studied:
In glove box, in the Schlenk bottle of drying, add 0.100g catalyzer, sealed by Schlenk bottle, shift out glove box rapidly, it is stand-by (at N to add 25.0g toluene
2to reflux 12h by metal Na under protection, existing steam existing with).Separately get several dry Schlenk reaction tubes, vacuum line is taken out inflated with nitrogen three times, add 10ml toluene under nitrogen atmosphere, then add quantitative ε-CL [ε-CL]
0: [Al]
0=500.Reaction tubes is put into oil bath and be heated to 80 DEG C respectively, 100 DEG C.Then add catalyzer toluene solution 7.50g under nitrogen atmosphere, start timing, at regular intervals, take out homogeneous reaction liquid 2-3ml with glass dropper under nitrogen atmosphere, and use acetic acid cancellation.Last directly to adding acetic acid in reaction tubes by whole reaction cancellation.The reaction solution obtained is drained solvent pass through
1h NMR test obtains monomer reaction transformation efficiency.To draining the polymer dissolution adding appropriate THF in thing and will obtain.Add proper amount of methanol, separate out polymkeric substance, adopt respectively and filter or centrifugal method, polymerisate is separated, finally by all polymer solids vacuum-drying obtained, then get 10mg sample, add after 5mlTHF dissolves 24h and carry out gel permeation chromatography (GPC) analysis with mark in polystyrene work, THF is solvent.
At gained 100 DEG C, reaction 4h, gained monomer conversion is more than 90%, obtain the number-average molecular weight of polymkeric substance between 30000-58800, and molecular weight distribution is between 1.30-1.42.Wherein the catalytic activity of compound 2a is best, and 100 DEG C time, monomer is 500 with catalyst concn ratio, and reaction 1.5h, monomer conversion can reach 61%, and the molecular weight distribution of polymkeric substance is 1.30.
Claims (10)
1. a class beta-diketon imido grpup alkoxyl group aluminum hydride compound, shown in the following I of its general structure:
In general formula I, Ar is the phenyl of phenyl or replacement; R is alkyl.
2. beta-diketon imido grpup alkoxyl group aluminum hydride compound as claimed in claim 1, it is characterized by Ar in general formula I is 2,6-diisopropyl phenyl.
3. beta-diketon imido grpup alkoxyl group aluminum hydride compound as claimed in claim 1, is characterized by substituent R in general formula I and is specially methyl.
4. beta-diketon imido grpup alkoxyl group aluminum hydride compound as claimed in claim 1, is characterized by substituent R in general formula I and is specially ethyl.
5. beta-diketon imido grpup alkoxyl group aluminum hydride compound as claimed in claim 1, is characterized by substituent R in general formula I and is specially sec.-propyl.
6. beta-diketon imido grpup alkoxyl group aluminum hydride compound as claimed in claim 1, is characterized by substituent R in general formula I and is specially benzyl.
7. beta-diketon imido grpup alkoxyl group aluminum hydride compound as claimed in claim 1, is characterized by substituent R in general formula I and is specially the tertiary butyl.
8. the synthetic method of beta-diketon imido grpup alkoxyl group aluminum hydride compound as claimed in claim 1, it is characterized by the compound with general formula I according to claim 1 is that compound by having following general structure II obtains through alcoholysis reaction, in general formula I I, substituent A r is specially 2,6-diisopropyl phenyl; Concrete synthetic method: under nitrogen protection;-78 DEG C ~ 100 DEG C conditions; preferably under 10 DEG C of-30 DEG C of conditions; to in the benzene of beta-diketon imido grpup aluminum hydride compound II or toluene or hexane solution; drip the alcohol of same molar, after being added dropwise to complete, remove a small amount of insoluble impurity after filtration; filtrate removes volatile matter under vacuum condition, and residuum is had the beta-diketon imido grpup alkoxyl group aluminum hydride compound of general structure I more as claimed in claim 1 with dry normal hexane recrystallization.
9. alcohol as claimed in claim 8 is methyl alcohol or ethanol or Virahol or benzylalcohol or the trimethyl carbinol.
10. the application of beta-diketon imido grpup alkylhydridosiloxanes aluminum compound as described in right 3 ~ 7, is characterized in that in toluene solution, the active ring-opening polymerization of catalysis 6-caprolactone under 70-110 DEG C of condition; Preferably under 100 DEG C of conditions, add the beta-diketon imido grpup alkylhydridosiloxanes aluminum compound as described in right 3 ~ 7 of 0.2% Mole percent amount, the transformation efficiency of 4 hours can more than 90%, and Polydispersity can be controlled in less than 1.42.
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Application publication date: 20141217 |