CN104725406B - Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester - Google Patents

Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester Download PDF

Info

Publication number
CN104725406B
CN104725406B CN201510032063.XA CN201510032063A CN104725406B CN 104725406 B CN104725406 B CN 104725406B CN 201510032063 A CN201510032063 A CN 201510032063A CN 104725406 B CN104725406 B CN 104725406B
Authority
CN
China
Prior art keywords
catalyst
binuclear aromatic
preparation
carbon dioxide
oxa
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201510032063.XA
Other languages
Chinese (zh)
Other versions
CN104725406A (en
Inventor
赵文善
李冬冬
王琪琳
卜站伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University
Original Assignee
Henan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan University filed Critical Henan University
Priority to CN201510032063.XA priority Critical patent/CN104725406B/en
Publication of CN104725406A publication Critical patent/CN104725406A/en
Application granted granted Critical
Publication of CN104725406B publication Critical patent/CN104725406B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06Zinc compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20General preparatory processes
    • C08G64/32General preparatory processes using carbon dioxide
    • C08G64/34General preparatory processes using carbon dioxide and cyclic ethers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a binuclear aromatic carboxylic acid zinc complex, wherein the structural formula thereof is shown in the description. The preparation method of the binuclear aromatic carboxylic acid zinc complex comprises the following steps: dissolving o-formyl-benzoic acid and 4-aminoantipyrene in ethanol, reacting at 20-80 DEG C for 1-5 hours, adding a methanol solution dissolved with Zn(OAc)2.2H2O, at this time, a large amount of white precipitates are generated in the reaction liquid, filtering and vacuum drying the precipitates at 60-120 DEG C; the molar ratio of the o-formyl-benzoic acid, the 4-aminoantipyrene and the Zn(OAc)2.2H2O is 1:1:(1-1.3). The binuclear aromatic carboxylic acid zinc complex is used as a catalyst to catalyze copolymerization of carbon dioxide and cyclohexene oxide to prepare polycarbonate cyclohexene ester. The catalyst has easily available raw materials, is simple in preparation method, stable in structure and is high in catalytic efficiency, and the Mw of the obtained polycarbonate cyclohexene ester is 60,000-170,000.

Description

Binuclear aromatic Zinc polycarboxylate composition, preparation method and its as catalyst preparation gather The application of cyclohexene carbonate
Technical field
The invention belongs to catalyst technical field is and in particular to a kind of binuclear aromatic Zinc polycarboxylate composition, preparation method And its application of polycyclohexene is prepared as catalyst carbon dioxide and 7-oxa-bicyclo[4.1.0 copolymerization.
Background technology
Carbon dioxide is a kind of greenhouse gases, is a kind of abundant, nontoxic, nonflammable c1 resource simultaneously again.Reduce dioxy Change carbon emission and using its be mankind's service be one of national strategic research problems of many.In the presence of catalyst, two The important channel that fatty poly-ester carbonate is chemical utilization carbon dioxide is prepared in carbonoxide and epoxide reaction.Dioxy Change carbon and the fatty poly-ester carbonate of epoxide copolymerization preparation is of many uses, can be used as engineering plastics, biodegradable nothing Contaminated materials, a sex medicine and packaging material for food, adhesive and composite etc..In numerous fatty poly-ester carbonates In, because carbon dioxide and 7-oxa-bicyclo[4.1.0 copolymerization preparation polycyclohexene have higher thermal degradation and vitrification turns Temperature, is increasingly subject to people's attention.Exploitation can be catalyzed efficiently urging of carbon dioxide and epoxide copolymerization Agent is significant.
1999, nozaki synthesized chiral bimetallic Zn complex, and these compounds can be in 40 DEG C, 3 mpa conditions Lower catalysis 7-oxa-bicyclo[4.1.0 prepares polycyclohexene with carbon dioxide copolymerization.Subsequently coates also reports this kind of catalyst (j. am. chem. soc., 1999,121,11008-11009;Chem. connum, 2000,2007- 2008). 2005, lee synthesized a series of benzeno connection beta-diimine bimetallic Zn complex, these coordination compounds 80 DEG C, 1.2 Carbon dioxide and 7-oxa-bicyclo[4.1.0 copolymerization can be catalyzed, its activity is apparently higher than monometallic beta-diimine base zinc gold under the conditions of mpa Metal complex (j. am. chem. soc., 2005,127,3031-3037).2007, limberg reported benzo pyrrole Mutter the beta-diimine base alkyl of bridging and sulphonyl bimetallic Zn complex, these coordination compounds are urged under the conditions of 75 DEG C, 0.8 mpa Change carbon dioxide and 7-oxa-bicyclo[4.1.0 polymerization (organometallices, 2007,26. 3668-3676).2009, Williams reports a series of robson type double-core and three core Zn complexes, and this kind of coordination compound can be urged in atmospheric conditions Change 7-oxa-bicyclo[4.1.0 and carbon dioxide copolymerization (inorg. chem. 2009,48,9535 9542; angew. chem. Int. ed. 2009,48,931 933).Harder etal. reports the bimetallic of the diketimine part with bridging Calcium and Zn complex, this kind of coordination compound has shown higher activity (cn to catalysis carbon dioxide and 7-oxa-bicyclo[4.1.0 copolymerization 103906571).But above-mentioned method all has different degrees of defect, thus limit it extensively applying.
Content of the invention
Present invention aim to overcome that prior art defect, there is provided a kind of binuclear aromatic Zinc polycarboxylate composition, preparation Method and its application preparing polycyclohexene as catalyst carbon dioxide and 7-oxa-bicyclo[4.1.0 copolymerization.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of binuclear aromatic Zinc polycarboxylate composition, its structural formula is as follows:
It is adjacent formylbenzoate condensation 4-AA Zn complex, and its molecule skeleton symbol is zn2 (c42h42n6o14).In this this coordination compound, containing two central ion zn (ii), each zn (ii) respectively with a h2O molecule and Four carboxyl o are connected, and form dual-core architecture.
The preparation method of above-mentioned binuclear aromatic Zinc polycarboxylate composition, its comprise the steps: by adjacent formylbenzoate, 4-AA is dissolved in ethanol, reacts 1-5 h in 20-80 DEG C, is subsequently adding dissolved with zn (oac)2·2h2The methanol of o Solution, now produces a large amount of white precipitates in reactant liquor, filter, and obtains final product after being deposited in 60-120 DEG C of vacuum drying;Described neighbour's first Acyl group benzoic acid, 4-AA and zn (oac)2·2h2The mol ratio of o is 1:1:1-1.3.
Specifically, adjacent formylbenzoate and the amount ratio of ethanol are 1g:100-200 ml, zn (oac)2·2h2O and first The amount ratio of alcohol is 1g:45-100 ml.
Above-mentioned binuclear aromatic Zinc polycarboxylate composition is prepared with 7-oxa-bicyclo[4.1.0 copolymerization as catalyst carbon dioxide The application of polycyclohexene.
Above-mentioned binuclear aromatic Zinc polycarboxylate composition is prepared with 7-oxa-bicyclo[4.1.0 copolymerization as catalyst carbon dioxide The application of polycyclohexene, particularly as follows: under catalyst existence condition, carbon dioxide and 7-oxa-bicyclo[4.1.0 (epoxy hexamethylene The addition of alkane accounts for the 1/10-1/5 of reactor volume;Carbon dioxide is then excessive in the reaction, specifically can pass through catalytic reaction Pressure is controlling the addition of carbon dioxide) copolymerization, catalyst amount is the 0.5-1% of 7-oxa-bicyclo[4.1.0 weight, catalytic reaction Temperature 80-120 DEG C, catalytic reaction pressure 2.0-5.0 mpa, catalytic reaction time 24-96 h.
Compared to the prior art, beneficial effects of the present invention: catalyst raw material is easy to get, preparation method is simple, Stability Analysis of Structures, High catalytic efficiency, is catalyzed gained polycyclohexenem w In 6-17 ten thousand, catalytic efficiency is up to 1248 g polymer/g zinc.Phase Other aromatic carboxylic acid Zn complexes are catalyzed with the polycyclohexene of gained, using catalyst carbon dioxide of the present invention Narrower with the polycyclohexene molecular weight distribution of 7-oxa-bicyclo[4.1.0 copolymerization preparation.
Brief description
Fig. 1 is the Fourier infrared spectrum figure using binuclear aromatic Zinc polycarboxylate composition of the present invention;
Fig. 2 is the proton nmr spectra using binuclear aromatic Zinc polycarboxylate composition of the present invention.
Specific embodiment
The present invention is described further by the following examples, but protection scope of the present invention not limited to this.
Embodiment 1
A kind of binuclear aromatic Zinc polycarboxylate composition, its structural formula is as follows:
The preparation method of above-mentioned binuclear aromatic Zinc polycarboxylate composition, it comprises the steps: to weigh 0.15 g(1 Mmol) adjacent formylbenzoate is dissolved in 15 ml ethanol, is slowly added into 15 ml and is dissolved with 0.20g(1 mmol under room temperature) 4- ammonia The ethanol solution of base phenazone, stirring reaction 1 hour, then be slowly added into 10 ml and be dissolved with 0.22 g(1 mmol) zinc acetate [zn(oac)2·2h2O] methanol solution, now have a large amount of white precipitates to produce in reactant liquor, filter, be deposited in 80 DEG C of vacuum 24 hs are dried and obtain 0.35 g white powdery solid (yield 73.9%), as binuclear aromatic Zinc polycarboxylate composition product, it is infrared See Fig. 1 and 2 with proton nmr spectra result, specific as follows:
): 1636 (ν c=o), 1588(ν-c=n), ftir(kbr 1394(ν coo-), 1474,762,746(ν ar) cm-1 .1H nmr(400 mhz, dmso): δ 10.19 (s ,-ch=n), 8.15-7.76 (m ,-ch), 7.60-7.24 (m, -ch), 3.16 (s, -n-ch3), 2.44 (s, -n-ch3),1.82(s, ch3coo-).
Embodiment 2
Above-mentioned binuclear aromatic Zinc polycarboxylate composition is prepared with 7-oxa-bicyclo[4.1.0 copolymerization as catalyst carbon dioxide The application of polycyclohexene, particularly as follows: take 0.10 g catalyst to put into the 100 ml rustless steel reaction under high pressures dried in advance In kettle, it is warming up to 100 DEG C of vacuum drying 2 h, is filled with carbon dioxide and is cooled to room temperature (in order to the air in replacement reaction kettle and water Vapour, makes reactor be under carbon dioxide atmosphere, similarly hereinafter).Add 10 ml epoxy hexamethylenes with glass syringe in reactor Alkane, is filled with carbon dioxide, after keeping pressure magnetic agitation reaction 24 h under the conditions of 4.0 mpa, 110 DEG C of temperature, stopped reaction, It is cooled to room temperature;
Product is removed, the complete 7-oxa-bicyclo[4.1.0 of Distillation recovery unreacted, residue from dichloromethane is dissolved, so Slowly instill afterwards in the enough methanol of high-speed stirred, be settled out high polymer, through filtration, methanol washing, vacuum drying, obtain poly- carbon Sour cyclohexene ester 9.86 g.Measuring its mw by gel permeation chromatography is 156500 g.mol-1, pdi is 1.95, warp1H nmr divides Analysis carbonic ester chain link content is 97.3%, and catalytic efficiency is 719g polymer/g zinc.
Embodiment 3
Above-mentioned binuclear aromatic Zinc polycarboxylate composition is prepared with 7-oxa-bicyclo[4.1.0 copolymerization as catalyst carbon dioxide The application of polycyclohexene, particularly as follows: take 0.10 g catalyst to put into the 100 ml rustless steel reaction under high pressures dried in advance In kettle, it is warming up to 100 DEG C of vacuum drying 2 h, is filled with carbon dioxide and is cooled to room temperature.Added in reactor with glass syringe 20 ml 7-oxa-bicyclo[4.1.0s, are filled with carbon dioxide, keep pressure magnetic agitation reaction 48 under the conditions of 2.0 mpa, 110 DEG C of temperature After h, stopped reaction, it is cooled to room temperature;
Product is removed, the complete 7-oxa-bicyclo[4.1.0 of Distillation recovery unreacted, residue from dichloromethane is dissolved, so Slowly instill afterwards in the enough methanol of high-speed stirred, be settled out high polymer, through filtration, methanol washing, vacuum drying, obtain poly- carbon Sour cyclohexene ester 14.3 g.Measuring its mw by gel permeation chromatography is 78600 g.mol-1, pdi is 2.12, warp1H nmr divides Analysis carbonic ester chain link content is 97.5%, and catalytic efficiency is 1043g polymer/g zinc.
Embodiment 4
Above-mentioned binuclear aromatic Zinc polycarboxylate composition is prepared with 7-oxa-bicyclo[4.1.0 copolymerization as catalyst carbon dioxide The application of polycyclohexene, particularly as follows: take 0.10 g catalyst to put into the 100 ml rustless steel reaction under high pressures dried in advance In kettle, it is warming up to 100 DEG C of vacuum drying 2 h, is filled with carbon dioxide and is cooled to room temperature.Added in reactor with glass syringe 20 ml 7-oxa-bicyclo[4.1.0s, are filled with carbon dioxide, keep pressure magnetic agitation reaction 48 under the conditions of 4.0 mpa, 110 DEG C of temperature After h, stopped reaction, it is cooled to room temperature;
Product is removed, the complete 7-oxa-bicyclo[4.1.0 of Distillation recovery unreacted, residue from dichloromethane is dissolved, so Slowly instill afterwards in the enough methanol of high-speed stirred, be settled out high polymer, through filtration, methanol washing, vacuum drying, obtain poly- carbon Sour cyclohexene ester 17.1 g.Measuring its mw by gel permeation chromatography is 140000 g.mol-1, pdi is 2.04, warp1H nmr divides Analysis carbonic ester chain link content is 98.1%, and catalytic efficiency is 1248g polymer/g zinc.
Embodiment 5
Above-mentioned binuclear aromatic Zinc polycarboxylate composition is prepared with 7-oxa-bicyclo[4.1.0 copolymerization as catalyst carbon dioxide The application of polycyclohexene, particularly as follows: take 0.10 g catalyst to put into the 100 ml rustless steel reaction under high pressures dried in advance In kettle, it is warming up to 100 DEG C of vacuum drying 2 h, is filled with carbon dioxide and is cooled to room temperature.Added in reactor with glass syringe 20 ml 7-oxa-bicyclo[4.1.0s, are filled with carbon dioxide, keep pressure magnetic agitation reaction 96 under the conditions of 4.0 mpa, 120 DEG C of temperature After h, stopped reaction, it is cooled to room temperature;
Product is removed, the complete 7-oxa-bicyclo[4.1.0 of Distillation recovery unreacted, residue from dichloromethane is dissolved, so Slowly instill afterwards in the enough methanol of high-speed stirred, be settled out high polymer, through filtration, methanol washing, vacuum drying, obtain poly- carbon Sour cyclohexene ester 16.6 g.Measuring its mw by gel permeation chromatography is 145500 g.mol-1, pdi is 2.09, warp1H nmr divides Analysis carbonic ester chain link content is 97.8%, and catalytic efficiency is 1210g polymer/g zinc.

Claims (5)

1. a kind of binuclear aromatic Zinc polycarboxylate composition, its structural formula is as follows:
.
2. the preparation method of binuclear aromatic Zinc polycarboxylate composition described in claim 1 is it is characterised in that comprise the steps: Adjacent formylbenzoate, 4-AA are dissolved in ethanol, react 1-5 h in 20-80 DEG C, be subsequently adding dissolved with zn (oac)2·2h2The methanol solution of o, now produces white precipitate in reactant liquor, filters, and precipitation obtains final product after being dried;Described neighbour's formyl Yl benzoic acid, 4-AA and zn (oac)2·2h2The mol ratio of o is 1:1:1-1.3.
3. the preparation method of binuclear aromatic Zinc polycarboxylate composition as claimed in claim 2 is it is characterised in that adjacent formoxyl benzene first Acid is 1g:100-200 ml, zn (oac) with the amount ratio of ethanol2·2h2O is 1g:45-100 ml with the amount ratio of methanol.
4. binuclear aromatic Zinc polycarboxylate composition described in claim 1 is common with 7-oxa-bicyclo[4.1.0 as catalyst carbon dioxide The application of poly- preparation polycyclohexene.
5. binuclear aromatic Zinc polycarboxylate composition as claimed in claim 4 is as catalyst carbon dioxide and 7-oxa-bicyclo[4.1.0 The application of polycyclohexene is prepared in copolymerization it is characterised in that catalyst amount is the 0.5-1% of 7-oxa-bicyclo[4.1.0 weight, Catalytic reaction temperature 80-120 DEG C, catalytic reaction pressure 2.0-5.0 mpa, catalytic reaction time 24-96 h.
CN201510032063.XA 2015-01-22 2015-01-22 Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester Expired - Fee Related CN104725406B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510032063.XA CN104725406B (en) 2015-01-22 2015-01-22 Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510032063.XA CN104725406B (en) 2015-01-22 2015-01-22 Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester

Publications (2)

Publication Number Publication Date
CN104725406A CN104725406A (en) 2015-06-24
CN104725406B true CN104725406B (en) 2017-02-01

Family

ID=53449882

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510032063.XA Expired - Fee Related CN104725406B (en) 2015-01-22 2015-01-22 Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester

Country Status (1)

Country Link
CN (1) CN104725406B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115028845B (en) * 2022-05-11 2023-05-12 烟台大学 Zinc coordination polymer catalyst and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780419B (en) * 2010-02-10 2011-10-19 南阳中聚天冠低碳科技有限公司 Zinc polycarboxylate composition catalyst and application for preparing aliphatic polycarbonate
CN101768261B (en) * 2010-02-10 2012-03-14 南阳中聚天冠低碳科技有限公司 Application of aromatic zinc carboxylate complex catalyst for preparing aliphatic polycarbonate

Also Published As

Publication number Publication date
CN104725406A (en) 2015-06-24

Similar Documents

Publication Publication Date Title
WO2008150033A1 (en) Epoxide-carbon dioxide stereoselective alternating copolymer
CN101186604B (en) One-step method for synthesizing lactone type crown ether by lactone ring expansion
CN102659850A (en) Tetradentate Schiff base metal complex, metal porphyrin complex and method for preparing polycarbonate
Vagnoni et al. Choline-based eutectic mixtures as catalysts for effective synthesis of cyclic carbonates from epoxides and CO2
CN102827136B (en) Method for preparing cyclic carbonate from carbon dioxide and epoxy compound through cycloaddition
CN102079737B (en) Method for preparing apigenin
CN112279825A (en) Preparation method of 5-halogenated methyl furfural
CN106916109B (en) A method of it protonating pyrazoles ionic liquid and utilizes its catalytically synthesizing cyclic carbonate ester
CN113999105A (en) Preparation method of hydroxyl acidic organic ligand
CN106045913A (en) Imidazolium perrhenate ionic liquid with amino groups as well as preparation method and application of imidazolium perrhenate ionic liquid
CN104725406B (en) Binuclear aromatic carboxylic acid zinc complex, preparation method and application thereof serving as catalyst to prepare polycarbonate cyclohexene ester
CN110078702A (en) A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate
CN107722254B (en) The catalyst and catalysis process for preparing fatty poly-ester carbonate are reacted with cyclohexene oxide for carbon dioxide
CN102030625A (en) Method for synthesizing vanillin
CN107641197B (en) It is a kind of using carbon dioxide and 7-oxa-bicyclo[4.1.0 as the copolyreaction catalyst of monomer
CN104262367A (en) Method for synthesizing aliphatic polycarbonate by catalyzing heterocyclic zinc carboxylate complex
Lv et al. A new Co-based metal-organic coordination polymer as a catalyst in chemical fixation of CO2
CN114685773A (en) Functionalized tin imidazolium salt catalyst, preparation method thereof and application of catalyst in synthesizing PES
CN114653404A (en) Ruthenium compound catalyst and application thereof in olefin metathesis
CN113399000B (en) Catalyst and preparation method thereof, catalyst composition and method for preparing straight-chain alcohol from epoxy compound
CN106565623B (en) A method of synthesis aromatic heterocycle formic ether compounds
CN102558196A (en) Method for preparing (3,4)-1,4-dioxoethylidene thiophene-2'-methanol
CN101633726B (en) Using method of catalyst in production process of polyethylene glycol terephthalate
CN109053785A (en) One kind is for being catalyzed CO2Hydrogenation reaction prepares homogeneous catalyst and its preparation method and the application of formates
CN116102726B (en) Chiral organoboron catalyst, preparation method thereof and application thereof in preparation of optically active polycarbonate or polyester

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170201

Termination date: 20180122

CF01 Termination of patent right due to non-payment of annual fee