CN102516279A - Compound containing aluminum core as well as preparation method and application thereof - Google Patents
Compound containing aluminum core as well as preparation method and application thereof Download PDFInfo
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- CN102516279A CN102516279A CN2011104209281A CN201110420928A CN102516279A CN 102516279 A CN102516279 A CN 102516279A CN 2011104209281 A CN2011104209281 A CN 2011104209281A CN 201110420928 A CN201110420928 A CN 201110420928A CN 102516279 A CN102516279 A CN 102516279A
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- LJEYADTXAXMEBG-UHFFFAOYSA-N CC[Al](CC)([N](C)(C)c1c(C2)cc(C)cc1)OC2(c1ccccc1)c1ccccc1 Chemical compound CC[Al](CC)([N](C)(C)c1c(C2)cc(C)cc1)OC2(c1ccccc1)c1ccccc1 LJEYADTXAXMEBG-UHFFFAOYSA-N 0.000 description 1
- UQXGAFPZEBHBQD-YTNSDAIYSA-N CC[Al](CC)([N](C)(C)c1c(C2)cc(C)cc1)O[C@@]2(C)c1ccccc1 Chemical compound CC[Al](CC)([N](C)(C)c1c(C2)cc(C)cc1)O[C@@]2(C)c1ccccc1 UQXGAFPZEBHBQD-YTNSDAIYSA-N 0.000 description 1
- 0 Cc(cc1)cc(C*O)c1N(C)C Chemical compound Cc(cc1)cc(C*O)c1N(C)C 0.000 description 1
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Abstract
The invention relates to a compound containing an aluminum core as well as a preparation method and an application thereof. The compound is prepared by reacting AlEt3 or AlMe3 with absolute ethanol according to a general formula I for 12-18 hours in an organic solvent at a temperature of 60 DEG C below zero to 80 DEG C, wherein the molar ratio of the AlEt3 or the AlMe3 to the absolute ethanol according to the general formula I is 3:2; and in the general formula I, R is alkylene, and Me is the abbreviation of methyl. The compound containing the aluminum core is used as a catalyst for Epsilon-caprolactone ring-opening polymerization.
Description
Technical field
The present invention relates to aluminum complex in, this aluminum complex can be used as the catalyzer of 6-caprolactone ring-opening polymerization, belongs to organometallics in the synthetic Application for Field of resin.
Background technology
Polyester fat lactone is one type of important thermoplastic plastic, and important use is arranged in medical material.Particularly poly-epsilon-caprolactone with gather gamma-butyrolactone, can also be doped among many other plastics, to its carry out modification (X.Zhang, U.P.Wyss, D.Pichora, M.F.A.Goosen, J.Macromol.Sci.Pure Appl.Chem.A30 (1993) 933; R.G.Sinclair, J.Macromol.Sci.Pure Appl.Chem.A33 (1996) 585; A.Duda, A.Kowalski, S.Penczek, H.Uyama, S.Kobayashi.Macromolecules 35 (2002) 4266).(poly-epsilon-caprolactone (PCL) that the ring-opening polymerization of ε-CL) obtains is example to 6-caprolactone, and it has high-crystallinity (can reach 69%) and good thermostability, and decomposition temperature is up to 350 ℃.Simultaneously, poly-epsilon-caprolactone is easy to again decomposed by mikrobe or enzyme under field conditions (factors), finally generates carbonic acid gas and water.Its good biodegradable and good biocompatibility, can with material blend such as starch, process the macromolecular material of fully biodegradable.
Condensation polymerization method and ring-opening polymerization method are the main method of synthetic polylactone.But; The reaction of direct polycondensation method is a balanced reaction, and a spot of water of the later stage of polycondensation is difficult to remove fully, often obtains oligopolymer; So less employing (Xie Deliang; The ginger mark, Yang Changzheng. alcohol acid causes the research [J] of 6-caprolactone ring-opening polymerization. polymer journal, 2000 (5): 532-537).The ring-opening polymerization method can obtain HMW, low dispersed polymkeric substance, uses on the lactone ring opening polymerization method so present most of polyester synthetic research work all concentrates on.
In 1979, people such as Gschwend H W under study for action, at N, N; N ', under the existence of N '-Tetramethyl Ethylene Diamine, 4; N, amino adjacent benzene ring hydrogen is pulled out in N-trimethylaniline and n-Butyl Lithium reaction; With the UVNUL MS-40 reaction, just hydrolysis obtains the amino alcohol part with separating at last again, but the kind of such amino alcohol part is less.And before the present invention, also not with 2,4, N, N-tetramethyl-aniline are the amino alcohol part of starting raw material preparation.
The report of the aluminum complex of existing amino alcohol part is less, and the aluminum complex of amino alcohol part seldom is used in the research of catalysis 6-caprolactone ring-opening polymerization.
Summary of the invention
The object of the present invention is to provide a kind of compound and preparation and application that contains aluminium nuclear.
The compound that contains aluminium nuclear of the present invention, it has following structural formula, and Me is the methyl abbreviation in the formula, and Ph is the phenyl abbreviation:
Or have a following structural formula:
Or have a following structural formula:
Or have a following structural formula:
The described compound method that contains the compound of aluminium nuclear may further comprise the steps:
In organic solvent, under-60-80 ℃, by formula I and AlEt
3Or AlMe
3And absolute ethanol reaction 12-18h makes its Chinese style I and AlEt
3Or AlMe
3And the mol ratio of absolute ethanol is 3: 2;
Its general structure I:
In the general formula I, R is an alkylidene group.
The general formula of alkylidene group R is shown in II or the III in the general formula I;
General formula I I:
Among the general formula I I, R
1And R
2Be respectively hydrogen, alkyl, phenyl, substituted-phenyl, naphthyl or fused ring aryl; Or R
1And R
2Be methyl, ethyl or phenyl; Or R
1Be methyl, R
2Be phenyl or Alpha-Naphthyl;
Or general formula III:
In the general formula III, n is 0,1,2,3 or 4.
Described organic solvent is normal hexane, toluene or THF.
The described compound that contains aluminium nuclear is used for the ring-opening polymerization catalyst of catalysis caprolactone; In toluene, THF, dichloromethane solution, the ring-opening polymerization of catalysis caprolactone under 15-110 ℃ of condition.
Used all kinds of SOLVENTS all needs the strict deoxygenation processing that dewaters in the preparation process of the compound that contains aluminium nuclear of the present invention, and all operations all carries out explanation no longer in addition in experiment under the condition of the anhydrous and oxygen-free of strictness.
The compound method of described general structure I is made up of two-step reaction:
(1) under the nitrogen protection, between-78 ℃ to 80 ℃, in N, N; N ', N '-Tetramethyl Ethylene Diamine exist down, compound V and lithium alkylide or phenyl lithium reaction 10 minutes to 8 hours; The compound IV that obtains directly is used for next step reaction without separating, wherein compound V and N, N; N ', the mol ratio of N '-Tetramethyl Ethylene Diamine is 1: 1.5, the mol ratio of compound V and lithium alkylide or phenyl lithium is 1: 1 to 1: 1.5;
(2) between-78 ℃ to 80 ℃, in organic solvent, with a last step obtain react 20 minutes after 6 hours without isolated compound IV and aldehydes or ketones; Pour reaction solution in excessive formic acid, acetic acid or hydrochloric acid hydrolysis, add hydrochloric acid to pH value, then add ether, ETHYLE ACETATE, methylene dichloride or trichloromethane, tell water less than 2; Water hydro-oxidation sodium water solution to pH value adds ether, ETHYLE ACETATE, methylene dichloride or trichloromethane again greater than 8, tells organic phase, and drying is filtered, and obtains formula I part with ETHYLE ACETATE or normal hexane recrystallization behind the desolventizing; Wherein the mol ratio of compound IV and aldehydes or ketones is 1: 1 to 1: 1.1;
Shown in VI:
Formula VI
With one type of amino alcohol part and aluminum alkyls reaction, can prepare a series of novel aluminum complexes; And then such aluminum complex can be used as the catalyzer of 6-caprolactone ring-opening polymerization.
Description of drawings
Fig. 1 contains the crystalline structure figure of the compound 1 of aluminium nuclear.
Fig. 2 contains the crystalline structure figure of the compound 7 of aluminium nuclear.
Fig. 3 contains the crystalline structure figure of the compound 8 of aluminium nuclear.
The practical implementation method
Embodiment 1:
Synthesizing of aluminum complex 1:
Under the nitrogen protection, at-78 ℃ to adding part HL
1(0.49g, 1.5mmol) with the 100ml Schlenk bottle of 20ml dry toluene in, add AlEt
3(0.21ml 1.8mmol), has a small amount of bubble to produce immediately, slowly is warming up to room temperature, then react 6 hours after, vacuum is removed adularescent solid residue behind the volatile impunty.Add 15ml toluene and make it dissolving, place 0 ℃ of following crystallization, obtain colourless bulk crystals 0.32g, yield is 51%.Fusing point: 148-150 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)-0.20(s，
3J
H-H＝8.0Hz，4H，2AlCH
2CH
3)，0.90(t，
3J
H-H＝8.0Hz，6H，2AlCH
2CH
3)，3.72(s，2H，ArCH
2C)，1.96(s，?3H，ArCH
3)，2.94(s，6H，NMe
2)，6.83-7.34(m，13H，ArH)。IR(Nujol，KBr，cm
-1)：2922.3(br)，1460.5(m)，1377.1(s)，723.0(m)。
The crystalline structure figure of compound 1 that contains aluminium nuclear is as shown in Figure 1:
Embodiment 2:
Synthesizing of aluminum complex 2:
Under the nitrogen protection, at-78 ℃ to adding part HL
2(0.54g, 2.0mmol) with the 100ml Schlenk bottle of 20.0ml dry toluene in, add AlEt
3(0.25ml 2.2mmol), has a small amount of bubble to produce immediately, slowly is warming up to room temperature, then react 6 hours after, vacuum is removed adularescent solid residue behind the volatile impunty.Add 15ml toluene and make it dissolving, place 0 ℃ of following crystallization, obtain colourless bulk crystals 0.21g, yield is 32%.Fusing point: 196-198 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)-0.30(q，
3J
H-H＝8.0Hz，2H，AlCH
2CH
3)，-0.09(q，
3J
H-H＝8.0Hz，2H，AlCH
2CH
3)，0.72(t，
3J
H-H＝8.0Hz，3H，AlCH
2CH
3)，1.02(t，
3J
H-H＝8.0Hz，3H，AlCH
2CH
3)，3.24(d，
2J
H-H＝14.3Hz，1H，ArCH
2C)，3.95(d，
2J
H-H＝14.3Hz，1H，ArCH
2C)，2.19(s，3H，ArCH
3)，1.70(s，3H，CCH
3)，2.57(s，6H，NMe
2)，6.69-7.48(m，8H，ArH)。IR(Nujol，KBr，cm
-1)：2923.7(br，s)，1461.3(s)，1377.1c(s)，723.1(m)。
Embodiment 3:
Synthesizing of aluminum complex 3:
Under the nitrogen protection, at-78 ℃ to adding part HL
3(0.48g, 1.5mmol) with the 100ml Schlenk bottle of 20ml dry toluene in, add AlMe
3(toluene solution 1.0M) has a small amount of bubble to produce immediately, slowly is warming up to room temperature for 1.8ml, 1.8mmol, then react 6 hours after, vacuum is removed adularescent solid residue behind the volatile impunty.Add 15ml toluene and make it dissolving, place 0 ℃ of following crystallization, obtain colourless bulk crystals 0.25g, yield is 42%.Fusing point: 210-212 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)-0.43(s，6H，Al(CH
3)
2)，4.08(d，
2J
H-H＝11.6Hz，1H，ArCH
2C)，3.95(d，
2J
H-H＝11.6Hz，1H，ArCH
2C)，1.76(s，3H，ArCH
3)，1.75(s，3H，CCH
3)，2.51(d，6H，NMe
2)，6.64-7.78(m，10H，ArH)。IR(Nujol，KBr，cm
-1)：2923.7cm
-1(br，s)，1460.5(m)，1377.1(m)，722.5(m)。
The crystalline structure figure of aluminum complex 7 is as shown in Figure 2:
Embodiment 4:
Synthesizing of aluminum complex 4:
Under the nitrogen protection, at-78 ℃ to adding part HL
4(0.49g, 2.0mmol) with the 100ml Schlenk bottle of 20ml dry toluene in, add AlMe
3(toluene solution 1.0M) has a small amount of bubble to produce immediately, slowly is warming up to room temperature for 0.24ml, 2.4mmol, then react 6 hours after, vacuum is removed adularescent solid residue behind the volatile impunty.Add 15ml toluene and make it dissolving, place 0 ℃ of following crystallization, obtain colourless bulk crystals 0.21g, yield is 34%.Fusing point: 184-186 ℃.1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)-0.51(s，6H，Al(CH
3)
2)，3.20(d，2H，ArCH
2C)，2.31(s，3H，ArCH
3)，2.61(s，6H，NMe
2)，1.46(m，10H，-(CH
2)
5-)，6.78-7.21(m，3H，ArH)。IR(Nujol，KBr，cm
-1)：2924.5cm-1(br，s)，1460.5c(m)，1377.1(s)，722.5(m)。
Claims (5)
1. one kind contains the compound that aluminium is examined, and it is characterized in that: it has following structural formula, and Me is the methyl abbreviation in the formula, and Ph is the phenyl abbreviation:
Or have a following structural formula:
Or have a following structural formula:
Or have a following structural formula:
2. the described compound method that contains the compound of aluminium nuclear of a claim 1 is characterized in that: may further comprise the steps:
In organic solvent, under-60-80 ℃, by formula I and AlEt
3Or AlMe
3And absolute ethanol reaction 12-18h makes its Chinese style I and AlEt
3Or AlMe
3And the mol ratio of absolute ethanol is 3: 2;
Its general structure I:
In the general formula I, R is an alkylidene group.
3. the compound method that contains the compound of aluminium nuclear as claimed in claim 2, it is characterized in that: the general formula of alkylidene group R is shown in II or the III in the general formula I;
General formula I I:
Among the general formula I I, R
1And R
2Be respectively hydrogen, alkyl, phenyl, substituted-phenyl, naphthyl or fused ring aryl; Or R
1And R
2Be methyl, ethyl or phenyl; Or R
1Be methyl, R
2Be phenyl or Alpha-Naphthyl;
Or general formula III:
In the general formula III, n is 0,1,2,3 or 4.
4. the compound method that contains the compound of aluminium nuclear as claimed in claim 2, it is characterized in that: described organic solvent is normal hexane, toluene or THF.
5. the described purposes that contains the compound of aluminium nuclear of claim 1 is characterized in that: the ring-opening polymerization catalyst that is used for the catalysis caprolactone; In toluene, THF, dichloromethane solution, the ring-opening polymerization of catalysis caprolactone under 15-110 ℃ of condition.
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Citations (5)
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|---|---|---|---|---|
| CN101302230A (en) * | 2007-05-09 | 2008-11-12 | 北京化工大学 | Synthesis and application of carbon bridged diketone monoimino aluminum complex |
| CN102206228A (en) * | 2011-03-29 | 2011-10-05 | 苏州大学 | Aluminum bimetal alkyl compound, and preparation method and application thereof |
| CN102250131A (en) * | 2010-05-20 | 2011-11-23 | 北京化工大学 | Dialkoxy aluminum complexe coordinated by beta-diketiminato ligand, its preparation method and application in epsilon-caprolactone ring-opening polymerisation |
| CN102268028A (en) * | 2011-05-23 | 2011-12-07 | 中国科学院长春应用化学研究所 | Metal complex catalyst for efficiently catalyzing polymerization of caprolactone and lactide |
| CN102268030A (en) * | 2011-05-26 | 2011-12-07 | 华东理工大学 | Nitrogen-containing bisphenol oxygen-based ligand binuclear aluminum compound and preparation method and application thereof |
-
2011
- 2011-12-15 CN CN2011104209281A patent/CN102516279A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302230A (en) * | 2007-05-09 | 2008-11-12 | 北京化工大学 | Synthesis and application of carbon bridged diketone monoimino aluminum complex |
| CN102250131A (en) * | 2010-05-20 | 2011-11-23 | 北京化工大学 | Dialkoxy aluminum complexe coordinated by beta-diketiminato ligand, its preparation method and application in epsilon-caprolactone ring-opening polymerisation |
| CN102206228A (en) * | 2011-03-29 | 2011-10-05 | 苏州大学 | Aluminum bimetal alkyl compound, and preparation method and application thereof |
| CN102268028A (en) * | 2011-05-23 | 2011-12-07 | 中国科学院长春应用化学研究所 | Metal complex catalyst for efficiently catalyzing polymerization of caprolactone and lactide |
| CN102268030A (en) * | 2011-05-26 | 2011-12-07 | 华东理工大学 | Nitrogen-containing bisphenol oxygen-based ligand binuclear aluminum compound and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| HARBI T. AL-MASRI等: "Synthesis and characterization of novel intramolecularly base-stabilized BEt2 and BEt derivatives:molecular structures of 1-Et2BOCPh2-2-NMe2C6H4,1-(CH3COO)EtBOOCCy2-2-NMe2C6H4 and BEt(1-OCPh2CH2-2-NMe2C6H4)2", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》, vol. 690, no. 2, 6 November 2004 (2004-11-06), pages 469 - 476 * |
| HARBI T. AL-MASRI等: "Synthesis, Characterization,and Crystal Structures of Novel Intramolecularly Base-Stabilized Borane Derivatives with Six- and Seven-Membered Chelate Rings", 《INORG. CHEM.》, vol. 43, 2 October 2004 (2004-10-02), pages 7162 - 7169 * |
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Application publication date: 20120627 |