CN101899061A - Synthesis for zinc complex containing ligands of N and O and application of zinc complex in catalysis of ring opening polymerization of caprolactone - Google Patents
Synthesis for zinc complex containing ligands of N and O and application of zinc complex in catalysis of ring opening polymerization of caprolactone Download PDFInfo
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- CN101899061A CN101899061A CN2009100850950A CN200910085095A CN101899061A CN 101899061 A CN101899061 A CN 101899061A CN 2009100850950 A CN2009100850950 A CN 2009100850950A CN 200910085095 A CN200910085095 A CN 200910085095A CN 101899061 A CN101899061 A CN 101899061A
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- complex
- caprolactone
- opening polymerization
- zinc complex
- catalysis
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Abstract
The invention provides the preparation for a zinc complex containing ligands of N and O and the application thereof. The complex is novel in structure and easy to prepare, can be obtained by reacting ligands with diethyl zinc, and can used as a catalyst for the ring opening polymerization of caprolactone to obtain polycaprolactone with a higher yield and a larger molecular weight.
Description
Technical field:
The invention belongs to the catalyst system field of caprolactone ring-opening polymerization, be specifically related to preparation and the application of such Zn complex that a class contains the Zn complex of [N, O] part.
Background technology:
Polycaprolactone (PCL) is that a class has the good physical and mechanical property and the biodegradable polymer of processibility.It is biodegradable under natural composting conditions, finally is converted into carbonic acid gas and water, thereby can be widely used as daily plastic, fiber, wrapping material etc.; Degradable, absorption have excellent biological compatibility in the Human Physiology environment, thereby are widely used in medical field again, as medicine controlled releasing, bone fracture internal fixation material, surgical sutures etc.Because therefore its having a wide range of applications property becomes the focus that people study.
In recent years, people have synthesized a large amount of metal complex catalysts and have been used for the ring-opening polymerization of catalysis caprolactone, but present research mainly concentrated on synthesizing of ligand metallic catalysts such as containing beta-keto diimide class and Salen class, to containing better simply [N, O] research of metal complexes of part is less, before present patent application work, also do not contain the report of ring-opening polymerization of the Zn complex catalysis caprolactone of this type of part.
Summary of the invention:
The Zn complex that the purpose of this invention is to provide a kind of containing of [N, O] part.
Another purpose of the present invention provides the purposes of the Zn complex of described containing of [N, O] part.
Technical scheme of the present invention is as follows:
1 one kinds of Zn complexes that contain [N, O] part, its chemical formula has following general structure:
2[Zn(OR
1NR
2)
2]·2[Zn(OR
1NR
2)Et]
In the formula:
R
1Represent alkyl or aryl;
R
2Represent alkyl or aryl.
2 according to claim 1 containing [N, O] part Zn complex, it is characterized in that this title complex is a kind of among the following 1a to 1f:
1a：R
1＝-CH
2-CH
2-，R
2＝C
6H
5；
1b：R
1＝-CH
2-CH
2-，R
2＝2，6-Me
2C
6H
3；
1c：R
1＝-CH
2-CH
2-，R
2＝2，6-
iPr
2C
6H
3；
1d：R
1＝-CH
2-CH
2-CH
2-，R
2＝C
6H
5；
1e：R
1＝-CH
2-CH
2-CH
2-，R
2＝2，6-Me
2C
6H
3；
1f：R
1＝-CH
2-CH
2-CH
2-，R
2＝2，6-
iPr
2C
6H
3；
Contain the Zn complex of [N, O] part, route and method are as follows:
React 12h in the zinc ethyl solvent at normal temperatures of this experiment with [N, O] part and qdx, the ethane of cancellation 6 molecules, volatile matter is removed in decompression, is contained the Zn complex of [N, O] part with the normal hexane recrystallization.
Among the above-mentioned preparation method, it is characterized in that reaction conditions is to stir under the room temperature among the preparation method.
Among the above-mentioned preparation method, it is characterized in that the used solvent of recrystallization is a normal hexane among the preparation method.
Above-mentioned [the N that contains, O] Zn complex of part, can the ring-opening polymerization of catalysis caprolactone, catalytic process is as follows: with title complex and caprolactone mol ratio is 1: 200-1: 1600, in 18-60 ℃ of anhydrous solvent system, reaction 2-12h uses the acetate cancellation, pour into polymer precipitation is come out, last polymkeric substance decompressing and extracting is to constant weight.
In the above-mentioned Zn complex catalysis caprolactone ring-opening polymerization process that contains [N, O] part, used anhydrous solvent can be aromatic hydrocarbons, and halohydrocarbon or ether are taken from toluene, methylene dichloride, tetrahydrofuran (THF) etc.
Advantage of the present invention and positively effect: of the present invention containing, the Zn complex of [N, O] part was easy to preparation, and catalytic activity is higher.
Description of drawings
Embodiment:
The specific embodiment of the invention is not limited to following embodiment.Embodiments of the invention can make the professional and technical personnel more fully understand the present invention.
Embodiment one:
Title complex 1b (R
1=-CH
2-CH
2-, R
2=2,6-Me
2C
6H
3) synthetic:
In the Schlenk bottle of 100ml, add compound 2-(2,6-dimethyl benzene amido) ethanol 0.61g (3.67mmol), add the dissolving of 15ml toluene.Add the toluene solution (7.40mmol) of the ZnEt2 of 3.7ml 2M with disposable syringe, solution neutrality is carved with bubble and emerges, and normal temperature stirs 12h down.Remove volatile matter under the decompression and obtain white solid, obtain bulk crystals 0.74g with the normal hexane recrystallization, productive rate is 62%.Fusing point is 115-117 ℃.
1HNMR(300MHz，CDCl
3，25℃，TMS)：δ(ppm)6.80-7.03(m，18H，ArH)，3.91-3.93(t，3JH-H＝3.0Hz，12H，CH
2CH
2O)，3.58(s，3H，NH)，3.42(s，3H，NH)，3.18-3.22(q，3JH-H＝3.0Hz，12H，CH
2CH
2N)，2.31(s，36H，C
6H
3(CH
3)
2)，-0.67--0.72(m，10H，ZnCH
2CH
3)。MS(EI)：m/z?164[2，6-Me
2(C
6H
3)NHCH
2CH
2O]
+，134[CH
2＝N-C
6H
3(CH
3)
2]
+，106[2，6-Me
2(C
6H
3)]
+，65[Zn]
+。IR?v?3045，1257，1102，766cm
-1。
Embodiment two:
Title complex 1b (R
1=-CH
2-CH
2-, R
2=2,6-Me
2C
6H
3) catalysis caprolactone ring-opening polymerization
With 10 is catalyzer catalysis caprolactone ring-opening polymerization under 18 ℃ and 60 ℃ of two kinds of temperature respectively.
A: under nitrogen protection; join in the 15ml exsiccant toluene as initiator with the toluene solution of disposable syringe 1.1ml 8.84Mm title complex 1b; then under appropriate reaction conditions; needle tubing with good airproof performance under nitrogen protection adds an amount of 6-caprolactone (226mg; 452mg; 900mg; 1810mg); make system react 12h down at 18 ℃; then respectively with acetic acid aqueous solution cancellation reaction; adding the stirring of 20ml hexane comes out polymer precipitation; polymkeric substance separates after filtration; room temperature vacuum-drying obtains white netted solid; output is respectively 210mg; 416mg; 791mg; 1430mg, productive rate is respectively 93%; 92%; 88%; 79%.Product characterizes with GPC.
B: under nitrogen protection; join in the 15ml exsiccant toluene as initiator with the toluene solution of disposable syringe 1.1ml 8.84Mm title complex 1b; then under appropriate reaction conditions; needle tubing with good airproof performance under nitrogen protection adds an amount of 6-caprolactone (900mg; 1810mg); make system react 2h down at 60 ℃; then respectively with acetic acid aqueous solution cancellation reaction; adding the stirring of 20ml hexane comes out polymer precipitation; polymkeric substance separates after filtration; room temperature vacuum-drying obtains colourless netted solid; output is respectively 810mg; 1500mg, productive rate is respectively 90%; 83%.Product characterizes with GPC.
Claims (6)
1. Zn complex that contains [N, O] part, its chemical formula has following general structure:
2[Zn(OR
1NR
2)
2]·2[Zn(OR
1NR
2)Et]
In the formula:
R
1Represent alkyl or aryl;
R
2Represent alkyl or aryl.
2. according to claim 1 containing [N, O] part Zn complex, it is characterized in that this title complex is a kind of among the following 1a to 1f:
1a：R
1＝-CH
2-CH
2-，R
2＝C
6H
5；
1b：R
1＝-CH
2-CH
2-，R
2＝2，6-Me
2C
6H
3；
1c：R
1＝-CH
2-CH
2-，R
2＝2，6-
iPr
2C
6H
3；
1d：R
1＝-CH
2-CH
2-CH
2-，R
2＝C
6H
5；
1e：R
1＝-CH
2-CH
2-CH
2-，R
2＝2，6-Me
2C
6H
3；
1f：R
1＝-CH
2-CH
2-CH
2-，R
2＝2，6-
iPr
2C
6H
3；
React 12h in the zinc ethyl solvent at normal temperatures of this experiment with [N, O] part and qdx, the ethane of cancellation 6 molecules, volatile matter is removed in decompression, is contained the Zn complex of [N, O] part with the normal hexane recrystallization.
3. among the above-mentioned preparation method, it is characterized in that reaction conditions is to stir under the room temperature among the preparation method.
4. among the above-mentioned preparation method, it is characterized in that the used solvent of recrystallization is a normal hexane among the preparation method.
5. above-mentioned [the N that contains, O] Zn complex of part, can the ring-opening polymerization of catalysis caprolactone, catalytic process is as follows: with title complex and caprolactone mol ratio is 1: 200-1: 1600, in 18-60 ℃ of anhydrous solvent system, reaction 2-12h uses the acetate cancellation, pour into polymer precipitation is come out, last polymkeric substance decompressing and extracting is to constant weight.
6. according to claim 2 containing [N, O] part Zn complex catalysis caprolactone ring-opening polymerization process in, used anhydrous solvent can be aromatic hydrocarbons, halohydrocarbon or ether are taken from toluene, methylene dichloride, tetrahydrofuran (THF) etc.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100850950A CN101899061A (en) | 2009-06-01 | 2009-06-01 | Synthesis for zinc complex containing ligands of N and O and application of zinc complex in catalysis of ring opening polymerization of caprolactone |
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Family
ID=43225016
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387283B (en) * | 2014-11-04 | 2016-06-08 | 济南大学 | A kind of four tooth nitrogen oxygen part and application thereof |
-
2009
- 2009-06-01 CN CN2009100850950A patent/CN101899061A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387283B (en) * | 2014-11-04 | 2016-06-08 | 济南大学 | A kind of four tooth nitrogen oxygen part and application thereof |
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| PB01 | Publication | ||
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Application publication date: 20101201 |