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 PDFInfo
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- 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
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- 239000011701 zinc Substances 0.000 title claims abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 9
- -1 cyclohexene ester Chemical class 0.000 title abstract description 10
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title abstract description 7
- 229920000515 polycarbonate Polymers 0.000 title abstract 3
- 239000004417 polycarbonate Substances 0.000 title abstract 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 67
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 33
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 229920005646 polycarboxylate Polymers 0.000 claims description 21
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- GNNILMDCYQGMRH-UHFFFAOYSA-N formyl benzoate Chemical group O=COC(=O)C1=CC=CC=C1 GNNILMDCYQGMRH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 abstract 2
- 229910007340 Zn(OAc)2.2H2O Inorganic materials 0.000 abstract 2
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 abstract 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 abstract 1
- 229960004424 carbon dioxide Drugs 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910000071 diazene Inorganic materials 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- XTUSLLYSMVWGPS-UHFFFAOYSA-N carbonic acid;cyclohexene Chemical compound OC(O)=O.C1CCC=CC1 XTUSLLYSMVWGPS-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SAOPTAQUONRHEV-UHFFFAOYSA-N gold zinc Chemical compound [Zn].[Au] SAOPTAQUONRHEV-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General 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
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.
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