CN101780419A - Zinc polycarboxylate composition catalyst and application for preparing aliphatic polycarbonate - Google Patents
Zinc polycarboxylate composition catalyst and application for preparing aliphatic polycarbonate Download PDFInfo
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- CN101780419A CN101780419A CN 201010110789 CN201010110789A CN101780419A CN 101780419 A CN101780419 A CN 101780419A CN 201010110789 CN201010110789 CN 201010110789 CN 201010110789 A CN201010110789 A CN 201010110789A CN 101780419 A CN101780419 A CN 101780419A
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Abstract
The invention discloses a preparation method by adopting carbon dioxide to be reacted with an epoxy compound to prepare aliphatic polycarbonate and an application method thereof. The catalyst is of O-carboxy benzaldehyde o-aminophenol zinc composition which is prepared by o-carboxy benzaldehyde, o-aminophenol and zinc acetate [Zn(OAc)2.2H2O] through reaction. By utilizing the catalyst, at the temperature of 60 to 180 DEG C and under the carbon dioxide pressure of 1.0 to 6.0 MPa, the carbon dioxide and the epoxy compound are catalyzed to be undertaken the copolymerization or terpolymer so as to obtain aliphatic polycarbonate with the molecular weight of 50000 to 190000 and different glass transition temperatures, and the maximum catalyzing efficiency can be of 1014 g polymer per one gram zinc.
Description
Technical field
The present invention relates to a kind of Zinc polycarboxylate composition catalyst, and be used to prepare the application of fatty poly-ester carbonate, carry out the application that binary or ternary polymerization prepare fatty poly-ester carbonate in particular for carbon dioxide and epoxide.
Background technology
Carbon dioxide is a kind of greenhouse gases, is again a kind of abundant Cl resource simultaneously.Minimizing CO2 emission, comprehensive utilization carbon dioxide have become important research project in this century.Utilize that carbon dioxide and epoxide reaction synthctic fat adoption carbonic ester method is simple, cost of material is low, the source is wide, is the important channel that chemistry utilizes carbon dioxide.The fatty poly-ester carbonate of carbon dioxide and epoxide copolymerization has light degradation and biological degradability, good blocking oxygen and the performance of water, can be used as engineering plastics, biodegradable nonpollution material, disposable medicine and packaging material for food, adhesive and composite etc., of many uses.But the effective catalyst of exploitation catalysis carbon dioxide and epoxide copolymerization is significant.
The catalyst that is used for catalysis carbon dioxide and epoxide prepared in reaction fatty poly-ester carbonate of report mainly contains (Coates G W such as zinc polycarboxylate class, phenoxy group zinc (cadmium), beta-diimine zinc, pyridine-zinc, (salen) MX, metalloporphyrin and corproporphyrin, double metal cyanide (DMC), rare earth, multi-nuclear metal complexes at present, et al.Angew Chem Int Ed, 2004,43,6618; SakakuraT, et al.Chem Rev, 2007,107,2365; Coates G W, et al US 2008/0051554; Fujimoto N, et al.US 2009/0240025; Wang Xianhong etc., CN 101402725; Lv Xiaobing etc., CN 101412809; Zhang Min etc., CN 101440159; Meng Yue is medium, and CN 1095403), wherein zinc polycarboxylate class catalyst system and catalyzing does not use organo-metallic compound, and operability is good, and the preparation method is simple, and is cheap, has better industrial application prospects.
(US 5 for United States Patent (USP), 026,676) provide one in the presence of organic solvent, utilize the method for the catalyst such as glutaric acid zinc, adipic acid zinc of zinc oxide and aliphatic dicarboxylic acid prepared in reaction, this catalyst carbon dioxide and expoxy propane copolymerization, catalytic efficiency are up to every gram catalyst and prepare the poly-propene carbonate of 26g.Through improved glutaric acid zinc catalyst (US 7,405,265) catalysis carbon dioxide and expoxy propane copolymerization, catalytic efficiency reaches the poly-propene carbonate of every gram catalyst preparation 77 grams.Glutaric acid zinc is (US 6,844,287) catalysis carbon dioxide and expoxy propane copolymerization after load, and catalytic efficiency reaches 358.8g polymer/g zinc.China applies for a patent (CN101058636) employing 2 is provided, 2`-biphenyl dicarboxylic acid and zinc acetate preparation 2, and the method for 2`-biphenyl dicarboxylic acid zinc catalyst, this catalyst carbon dioxide and 7-oxa-bicyclo[4.1.0 copolymerization, catalytic efficiency is 653g polymer/g zinc.
Summary of the invention
One of purpose of the present invention provides a kind of Catalysts and its preparation method that is used to prepare fatty Merlon.
Another object of the present invention provides a kind of use catalyst carbon dioxide of the present invention and epoxide carries out binary or binary polymerization, prepares the method for fatty poly-ester carbonate.
Technical scheme of the present invention is as follows:
A kind of Zinc polycarboxylate composition catalyst that is used to prepare fatty poly-ester carbonate, this catalyst are the 2-carboxybenzaldehyde o-aminophenol Zn complex that contracts, and its molecular formula skeleton symbol is Zn (C
14H
9NO
3), architectural feature is:
In this composition catalyst, central ion Zn (II) takes the four-coordination mode, links to each other with two carboxyl O with a N, a hydroxyl O respectively; Carboxyl is taked the bidentate coordination, links to each other with two Zn (II) respectively; N represents that this complex is a Coordination Polymers, the multiple-unit aggregate number of basic structural unit in its numeric representation complex, and n=2～100, wherein n is preferably 2-20.
The method for preparing this catalyst is to add 2-carboxybenzaldehyde, o-aminophenol and zinc acetate [Zn (OAc) in solvent respectively
22H
2O], after the reaction after filtration, drying, prepare Zinc polycarboxylate composition catalyst.
The solvent that the preparation catalyst uses is methyl alcohol, ethanol, isopropyl alcohol, water or its mixture.
During the preparation catalyst, 2-carboxybenzaldehyde, o-aminophenol, zinc acetate [Zn (OAc)
22H
2O] mol ratio be 1: 1: 1～1.2, the reaction time is 0.5～5h, reaction temperature is room temperature～100 ℃, reaction finishes the back and filters, collect pulverulent solids,, promptly obtain the 2-carboxybenzaldehyde o-aminophenol Zn complex catalyst that contracts through 60～120 ℃ of vacuum drying.
Catalyst of the present invention is faint yellow to yellow powder, stable in the air.
Use the method for Preparation of Catalyst fatty poly-ester carbonate of the present invention to be, under above-mentioned Zinc polycarboxylate composition catalyst existence condition, carbon dioxide and epoxide copolymerization, catalyst amount is 0.01～1% of an epoxy compound amount; Reaction temperature is 60～180 ℃; Reaction pressure is 1.0～6.0MPa; Reaction time 20～120h.
The epoxide that the preparation fatty poly-ester carbonate uses is 7-oxa-bicyclo[4.1.0, expoxy propane or its mixture.
Compared with prior art, the invention has the advantages that the catalyst raw material is easy to get, the preparation method is simple, Stability Analysis of Structures, catalytic efficiency height.Utilize Preparation of Catalyst fatty poly-ester carbonate of the present invention, simple to operate, by regulating different raw material proportionings, can obtain the high polymer of serial different glass transition temperature.
The specific embodiment
Below in conjunction with embodiment the present invention is further described, but is not limited to the following example.
Embodiment 1
The contract preparation of o-aminophenol Zn complex of catalyst 2-carboxybenzaldehyde.
Taking by weighing 2-carboxybenzaldehyde 0.15g (1mmol) is dissolved in the 15mL ethanol, slowly add 15mL under the room temperature and be dissolved with the ethanolic solution of 0.11g (1mmol) o-aminophenol, stirred 15 minutes, and slowly added 10mL again and be dissolved with 0.22g (1mmol) zinc acetate [Zn (OAc)
22H
2O] methanol solution, have a large amount of yellow mercury oxides to produce immediately, filter, 80 ℃ of vacuum drying 5h, 0.25g yellow powder shape solid, yield 81.9%.IR(KBr)：1584(νC＝N)，1547(ν
asCOO
-)，1411(ν
sCOO
-)，1411(ν
sCOO
-)，1474、759、736(νAr)cm
-1。
Embodiment 2
The contract preparation of o-aminophenol Zn complex of catalyst 2-carboxybenzaldehyde.
Taking by weighing 2-carboxybenzaldehyde 0.15g (1mmol) is dissolved in the 10mL methyl alcohol, slowly add 10mL under the room temperature and be dissolved with the methanol solution of 0.11g (1mmol) o-aminophenol, stirring mixes it, slowly adds 10mL again and is dissolved with 0.23g (1.1mmol) zinc acetate [Zn (OAc)
22H
2O] methanol solution, have a large amount of yellow mercury oxides to produce immediately, filter, 60 ℃ of vacuum drying 5h, 0.26g yellow powder shape solid, yield 85.2%.IR(KBr)：1584(νC＝N)，1547(ν
asCOO
-)，1411(ν
sCOO
-)，1411(ν
sCOO
-)，1474、759、736(νAr)cm
-1。
Embodiment 3
0.10 catalyst and stirrer are put into the 100mL stainless steel autoclave of oven dry in advance, be warming up to 100 ℃, vacuum drying 6h charges into carbon dioxide to normal pressure.Add the 10mL 7-oxa-bicyclo[4.1.0 with glass syringe in reactor, charge into carbon dioxide, pressure remains on 4.0MPa, behind 90 ℃ of magnetic agitation reaction 40h, stops reaction, is chilled to room temperature.
Product is shifted out, unreacted 7-oxa-bicyclo[4.1.0 is reclaimed in distillation, and residue is also slowly splashed in the capacity methyl alcohol of high-speed stirred with an amount of carrene dissolving, is settled out high polymer, after filtration, methanol wash, vacuum drying, obtain fatty poly-ester carbonate 6.86g.By its mean molecule quantity of gel permeation chromatography is 186500, warp
1It is 94.3% that H NMR analyzes carbonic ester chain link content, and catalytic efficiency is 322g polymer/g zinc.
Embodiment 4
In the equipment identical with use among the embodiment 3, the addition of 7-oxa-bicyclo[4.1.0 is 20mL under identical condition, at 110 ℃, keep-up pressure and be 4.2MPa, reaction 60h obtains fatty poly-ester carbonate 16.0g, and its mean molecule quantity is 82600, carbonic ester chain link content is 96.5%, and catalytic efficiency is 751g polymer/g zinc.
Embodiment 5
In the equipment identical with use among the embodiment 3, the addition of 7-oxa-bicyclo[4.1.0 is 20mL under identical condition, at 110 ℃, keep-up pressure and be 4.5MPa, reaction 80h obtains fatty poly-ester carbonate 21.6g, and its mean molecule quantity is 71200, carbonic ester chain link content is 95.2%, and catalytic efficiency is 1014g polymer/g zinc.
Embodiment 6
In the equipment identical with use among the embodiment 3, the addition of 7-oxa-bicyclo[4.1.0 is 15mL under identical condition, the amount that adds expoxy propane is 5mL, and at 120 ℃, keep-uping pressure is 4.2MPa, reaction 80h, obtaining fatty poly-ester carbonate 5.0g, have only one with its glass transition temperature of dsc analysis, is 78.1 ℃, its mean molecule quantity is 57300, and catalytic efficiency is 235g polymer/g zinc.
Claims (7)
1. Zinc polycarboxylate composition catalyst is characterized in that described catalyst is the 2-carboxybenzaldehyde o-aminophenol Zn complex that contracts, and its molecular formula is Zn (C
14H
9NO
3), architectural feature is:
In this composition catalyst, central ion Zn (II) takes the four-coordination mode, links to each other with two carboxyl O with a N, a hydroxyl O respectively; Carboxyl is taked the bidentate coordination, links to each other with two Zn (II) respectively; N represents that this complex is a Coordination Polymers, the multiple-unit aggregate number of basic structural unit in its numeric representation complex, n=2～100.
2. Preparation of catalysts method according to claim 1 is characterized in that adding respectively 2-carboxybenzaldehyde, o-aminophenol and zinc acetate [Zn (OAc) in solvent
22H
2O], filter the reaction back, drying, prepares described Zinc polycarboxylate composition catalyst.
3. method according to claim 2, when it is characterized in that preparing catalyst, 2-carboxybenzaldehyde, o-aminophenol, zinc acetate [Zn (OAc)
22H
2O] mol ratio be 1: 1: 1～1.2, the reaction time is 0.5～5h, reaction temperature is room temperature～100 ℃.
4. method according to claim 2, it is characterized in that preparing the solvent that catalyst uses is respectively methyl alcohol, ethanol, isopropyl alcohol, water or its mixture.
5. application of using the described Preparation of Catalyst fatty poly-ester carbonate of claim 1 is characterized in that requiring 1 catalyst to be used for by carbon dioxide and epoxide copolymerization fatty poly-ester carbonate as catalyst profit.
6. according to the application of claim 5, it is characterized in that catalyst amount is 0.01～1% of an epoxy compound amount, reaction temperature is 60～180 ℃, and reaction pressure is 1.0～6.0MPa, reaction time 20～120h.
7. according to the application of claim 5, it is characterized in that preparing the epoxide that fatty poly-ester carbonate uses and be 7-oxa-bicyclo[4.1.0, expoxy propane or its mixture.
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|---|---|---|---|---|
| CN104725406A (en) * | 2015-01-22 | 2015-06-24 | 河南大学 | Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester |
| CN106008949A (en) * | 2016-06-28 | 2016-10-12 | 田东县浙缘农业科技有限公司 | Preparation and application of zinc dicarboxylate catalyst containing imine groups |
| CN107325021A (en) * | 2017-06-28 | 2017-11-07 | 哈尔滨理工大学 | O-aminophenol schiff bases and its synthetic method and application |
| CN113056330A (en) * | 2018-12-21 | 2021-06-29 | Lg化学株式会社 | Method for regenerating waste organic zinc catalyst by surface modification |
| CN115028824A (en) * | 2022-06-10 | 2022-09-09 | 浙江恒丰新材料有限公司 | Preparation method of carbon dioxide-based polycarbonate polyol product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725406A (en) * | 2015-01-22 | 2015-06-24 | 河南大学 | Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester |
| CN106008949A (en) * | 2016-06-28 | 2016-10-12 | 田东县浙缘农业科技有限公司 | Preparation and application of zinc dicarboxylate catalyst containing imine groups |
| CN106008949B (en) * | 2016-06-28 | 2019-03-08 | 田东县浙缘农业科技有限公司 | A kind of preparation and its application of the binary zine carboxylate catalyst containing imine group |
| CN107325021A (en) * | 2017-06-28 | 2017-11-07 | 哈尔滨理工大学 | O-aminophenol schiff bases and its synthetic method and application |
| CN107325021B (en) * | 2017-06-28 | 2019-04-26 | 哈尔滨理工大学 | O-aminophenol schiff bases and its synthetic method and application |
| CN113056330A (en) * | 2018-12-21 | 2021-06-29 | Lg化学株式会社 | Method for regenerating waste organic zinc catalyst by surface modification |
| US11944961B2 (en) | 2018-12-21 | 2024-04-02 | Lg Chem, Ltd. | Method for regenerating waste organic zinc catalyst through surface modification |
| CN113056330B (en) * | 2018-12-21 | 2024-05-14 | Lg化学株式会社 | Method for regenerating waste organozinc catalyst by surface modification |
| CN115028824A (en) * | 2022-06-10 | 2022-09-09 | 浙江恒丰新材料有限公司 | Preparation method of carbon dioxide-based polycarbonate polyol product |
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