CN101440159B - Process for synthesizing aliphatic polycarbonate - Google Patents
Process for synthesizing aliphatic polycarbonate Download PDFInfo
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- CN101440159B CN101440159B CN2008102200825A CN200810220082A CN101440159B CN 101440159 B CN101440159 B CN 101440159B CN 2008102200825 A CN2008102200825 A CN 2008102200825A CN 200810220082 A CN200810220082 A CN 200810220082A CN 101440159 B CN101440159 B CN 101440159B
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Abstract
The invention discloses a method for synthesizing aliphatic polycarbonate. The method comprises the following steps of putting double metal cyanide catalyst, carbon dioxide and epoxide into a high-pressure reactor, well mixing and heating the materials for catalytic reaction and obtaining a copolymer, wherein the apparent crystallinity of the double metal cyanide, which is obtained by use of X-ray powder diffraction characterization, is more than or equal to 70 percent. The high-crystallinity double metal cyanide catalyst used in the method has higher catalytic activity in the reaction of the carbon dioxide and propylene oxide, thereby overcoming the technical bias that the catalytic activity of crystalline-state double metal cyanide is generally considered to be lower than that of amorphous double metal cyanide in the field.
Description
Technical field
The present invention relates to chemosynthesis technical field, being specifically related to a kind of is catalyzer with the double metal cyanide, with the method for carbonic acid gas and the synthetic middle aliphatic polycarbonate with high molecular weight of epoxide.
Background technology
Double metal cyanide is general epoxide homopolymerization catalyzer, it synthetic generally all is to react in the aqueous solution with metal-salt and metal cyanide salt, add that organic ligand obtains, its synthetic technology has been open in patent documentations such as JP4145123, US5470813, EP700949, WO97/40086 and CN1255074.By changing the kind of metal and organic ligand, present double metal cyanide is used for the epoxide homopolymerization and can obtains quite high catalytic activity.And it is generally acknowledged that the double metal cyanide of low crystallization or even amorphous just can be obtained catalytic effect preferably, wherein degree of crystallinity is with having or not many sharp-pointed characteristic peaks to characterize among the X-ray powder diffraction figure.Bayer AG disclosed the synthetic method of the double metal cyanide of amorphous in 2005 among the disclosed patent documentation CN1762592A, it is amorphous to think that high activity double-metal prussiate comes down to.And the document that other is published has also proved this viewpoint, as (Hua Zhengjiang such as Hua Zhengjiang, old first-class, " form of double metal cyanide catalyst and to the influence of catalyst activity " journal of Zhejiang university (version of science), 2004,31 (1): 74-78.) thinking unbodied bimetallic cyaniding complex than the high reactivity that demonstrates of crystallization shape, should be the direction of following this type of catalyzer development.And another piece document (Chen S.et al. " Fe/Zn double metal cyanide catalyzed ring-opening polymerization of propyleneoxide:2.Characterization of active structure of double metal cyanide catalysts ", Colloid Polym Sci, 2004, point out that highly active DMC catalysts should have low degree of crystallinity in 282:1033-1038.).
Double metal cyanide is used for carbonic acid gas and epoxide copolymerization since the eighties in last century, complex compound as U.S. Pat 4500704 usefulness iron zinc cyanides and diglyme is used for carbonic acid gas and propylene oxide, catalytic efficiency is compared very low with the epoxide homopolymerization, only be 44 gram polymkeric substance/gram catalyzer.And the Chinese patent ZL 89100701 of Chen Liban etc. 1989 application is the copolymerization that catalyzer carries out carbonic acid gas and propylene oxide with the double metal cyanide of polymkeric substance load, and catalytic efficiency is brought up to 100 and restrained polymkeric substance/more than the gram catalyzer.Because part is a polymkeric substance, so this catalyzer is an amorphous.
Complex catalysis carbonic acid gas and propylene oxide copolymerization with the cobalt zinc cyanide and the trimethyl carbinol in 2004 such as Chen Shang obtain the lower molecular weight aliphatic polycarbonate, and Mn is between 2600-4000 for its number-average molecular weight, and catalytic efficiency is about 2000 gram polymkeric substance/gram catalyzer.Think in the literary composition that the reason of high catalytic efficiency is to have obtained noncrystalline state catalyzer (Chen S, Hua ZJ, Fang Z, Qi GR.Copolymerization of carbon dioxideand propylene oxide with highly effective zinc hexacyanocobaltate (III)-basedcoordination catalyst, Polymer, 2004,45:6519-6524).The catalyzer of same noncrystalline state also is used to carbonic acid gas and the cyclohexene oxide copolymerization obtains 20000 catalytic efficiencies that restrain about polymkeric substance/gram catalyzer.(Chen?S，Qi?GR，Hua?ZJ，Yan?HQ.Double?metal?cyanide?complexbased?on?Zn3[Co(CN)6]2as?highly?active?catalyst?for?copolymerization?of?carbondioxide?and?cyclohexene?oxide，J.Polym.Sci.，Part?A：Polymer?Chemistry，2004，42：5284-5291)
Though old going up obtained progress preferably in the application of DMC catalysts at carbon dioxide copolymerization, but only can be applied to the copolymerization of carbonic acid gas and propylene oxide, carbonic acid gas and cyclohexene oxide, the catalytic efficiency that wherein is applied to carbonic acid gas and propylene oxide is still on the low side, only 2000 gram polymkeric substance/gram catalyzer.And because oxyethane is extremely active, easily homopolymerization is difficult to realize itself and the copolymerization of carbonic acid gas, and other type catalyst catalytic efficiency of being used for carbonic acid gas and oxyethane all restrains polymkeric substance/below the gram catalyzer 100 at present.
Summary of the invention
At thinking in the prior art that the double metal cyanide of amorphous double metal cyanide than crystal form has the more technology prejudice of high catalytic activity, the purpose of this invention is to provide a kind of high-crystallinity DMC catalysts polymerization carbonic acid gas and epoxide of utilizing, obtain the method for number-average molecular weight in the middle aliphatic polycarbonate with high molecular weight more than 10000, the high-crystallinity DMC catalysts has shown higher catalytic activity in this method.
Purpose of the present invention realizes by following technical scheme: a kind of synthetic method of aliphatic polycarbonate is with DMC catalysts, carbonic acid gas and the epoxide autoclave of packing into, stirs, and catalyzed reaction is carried out in heating, obtains multipolymer;
Described double metal cyanide characterizes with X-ray powder diffraction, has sharp-pointed characteristic spectral line, and apparent degree of crystallinity should surpass 70%.
Be better implement the present invention, optimized technical scheme further is provided.
In the above-mentioned synthetic method, preferred 60～120 ℃ of the temperature of described catalyzed reaction, preferred 5～200h of reaction times; Between the weight ratio of described DMC catalysts and epoxide preferred 1: 500～20000; Preferred 0.5～the 10MPa of the pressure of described carbonic acid gas, more preferably 2～5MPa.
In the above-mentioned synthetic method, the mixture of one or more in described epoxide optimization ethylene oxide, propylene oxide, epoxy chloropropane, butylene oxide ring, cyclohexene oxide or the Styrene oxide 98min..
In the above-mentioned synthetic method, described DMC catalysts is preferably by the preparation of following method: soluble metal M1 halogenide or itself and the mixture of M1 oxide compound or M1 oxyhydroxide and the cyanide complex of another kind of soluble metal M2 are reacted in the mixed solvent of water or organic ligand and water, the precipitation that obtains is the mixed solvent washing of water or organic ligand and water again, obtain solid with centrifugal or filtering method, vacuum-drying obtains DMC catalysts again;
Described M1 and M2 are Al, Zn, and Co, Fe, Ni, Mn, Mo, V or Cu, wherein the mol ratio of M1/M2 is 1.5-4;
Described organic ligand preferred alcohols, mercaptan, phenol, ether, imines or organo phosphorous compounds.
In the above-mentioned synthetic method, for obtaining the more good described DMC catalysts of performance, more preferably following preparation method: the cyanide complex of soluble metal M2 formation solution A soluble in water, the mixture of soluble metal M1 halogenide or itself and M1 oxide compound or M1 oxyhydroxide is dissolved in the mixed solvent of organic ligand and water and forms solution or suspension liquid B, wherein the volume ratio of organic ligand and water is 3: 1-1: 3; B slowly splashed among the A react, temperature of reaction is 20-50 ℃; The precipitation that obtains is the mixed solvent washing of water or organic ligand and water again, and wherein the ratio of organic ligand and water is 3: 1-1: 3, obtain solid with centrifugal or filtering method, and obtain DMC catalysts in 20-50 ℃ of vacuum-drying again.
Among the preparation method of above-mentioned DMC catalysts, described M1 is Zn more preferably; Described M2 is Co, Ni or Fe more preferably; Described organic ligand is alcohol or ether more preferably, as Virahol, and propyl carbinol, isopropylcarbinol, the trimethyl carbinol, ethylene glycol, glycerine, glyme, diglyme, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, special preferred tertiary butanols and glyme.
The aliphatic polycarbonate that above-mentioned synthetic method obtains, has aliphatic carbon chain on the main chain chain link, repeating unit is the polymkeric substance of carbonic ether, be with or without aromatic nucleus on its side chain, comprise polymerized thylene carbonate ethyl ester, poly (propylene carbonate), polymerized thylene carbonate butyl ester, the inferior cyclohexyl of poly-carbon ester or polymerized thylene carbonate phenethyl ester, its number-average molecular weight sees through the numerical value of chromatogram (GPC) method sign more than 10000 with gel.
Compared with prior art, the present invention has following beneficial effect:
(1) compares (Chen S with the catalyzer of old first-class report, Hua ZJ, Fang Z, Qi GR.Copolymerization of carbon dioxide and propylene oxide with highly effective zinchexacyanocobaltate (III)-based coordination catalyst, Polymer, 2004,45:6519-6524), the DMC catalysts of the high-crystallinity of the present invention's preparation has higher catalytic activity in carbonic acid gas and propylene oxide reaction, catalytic efficiency is at 8000 gram polymkeric substance/more than the gram catalyzer, overcome this area and generally believed that the catalytic activity of crystal form double metal cyanide will be lower than the technology prejudice of non-crystalline state double metal cyanide.
(2) DMC catalysts energy catalysis carbonic acid gas and oxyethane, carbonic acid gas and the Styrene oxide 98min. copolymerization of the present invention's preparation, catalytic efficiency is at 1000 gram polymkeric substance/more than the gram catalyzer, this does not appear in the newspapers in the prior art, has expanded the Application Areas of DMC catalysts.
Description of drawings
Fig. 1 is the X-ray powder diffraction figure of the Zn-Co DMC catalysts among the embodiment 1.
Fig. 2 is the IR collection of illustrative plates of the polymerized thylene carbonate ethyl ester among the embodiment 4.
Fig. 3 is the polymerized thylene carbonate ethyl ester among the embodiment 4
1The HNMR collection of illustrative plates.
Embodiment
Below in conjunction with specific embodiments and the drawings the present invention is further described, but be not limited only to following examples.
Embodiment 1-3 is the preparation of the used DMC catalysts of the present invention
The 0.01mol potassium hexacyanocobaltate is dissolved in the 50mL water, the 0.3mol zinc chloride is dissolved in 150mL water and the 50mL trimethyl carbinol mixed solution.Under vigorous stirring, 20 ℃ slowly splash into potassium hexacyanocobaltate solution in the liquor zinci chloridi, generate that post precipitation continues vigorous stirring so that the part trimethyl carbinol and the abundant complexing of precipitation.Centrifugation afterwards precipitation, the gained precipitation is changed slurry again with the mixed solution of 1: 3 trimethyl carbinol of volume ratio and water, and repeated centrifugation and change are washed and starched and are washed repeatedly, progressively improve the volume ratio to 3 of butanol/water: 1.At last, till centrifugate can not detect potassium ion with potassium reagent.Dry 100h obtains the Zn/Co DMC catalysts in 20 ℃ the vacuum drying oven with being deposited in, and its structural formula is (Zn)
2.82[Co (CN)
7.38] Cl
0.49L
1.32(OH)
2.27(H
2O)
0.04X-ray diffraction records its degree of crystallinity in (as shown in Figure 1) more than 70%.
The organic ligand trimethyl carbinol can be substituted by other alcohol or ethers in the present embodiment, as Virahol, and propyl carbinol, isopropylcarbinol, ethylene glycol, glycol ether, glycerine, glyme, diglyme, ethylene glycol monomethyl ether, ethylene glycol ethyl ether; Also can substitute by imine compound.
0.01mol Hexacyanoferrate potassium is dissolved in the 50mL water, 0.5mol zinc oxide and zinc chloride are dissolved in 150mL water and the 150mL trimethyl carbinol mixed solution.Under vigorous stirring, 30 ℃ slowly splash into the Hexacyanoferrate potassium solution in zinc oxide and the zinc chloride mixing solutions, generate that post precipitation continues vigorous stirring so that the part trimethyl carbinol and the abundant complexing of precipitation.Filtering separation precipitation afterwards, the gained precipitation is changed slurry again with the mixed solution of 1: 3 trimethyl carbinol of volume ratio and water, and repeated centrifugation and change are washed and starched and are washed repeatedly, and increase the ratio to 3 of butanol/water in the washings one by one: 1.At last, till centrifugate can not detect potassium ion with potassium reagent.Dry 45h obtains the Zn/Fe DMC catalysts in 50 ℃ the vacuum drying oven with being deposited in, and its structural formula is (Zn)
1.96[Fe (CN)
5.66] Cl
0.09L
0.9(OH)
0.34(H
2O)
1.63X-ray diffraction records its degree of crystallinity more than 70%.
The organic ligand trimethyl carbinol can be substituted by other alcohol or ethers in the present embodiment, as Virahol, and propyl carbinol, isopropylcarbinol, ethylene glycol, glycerine, glycol ether, glyme, diglyme, ethylene glycol monomethyl ether, ethylene glycol ethyl ether; Can also substitute by thio-alcohol or phenolic compound.
The 0.01mol potassium tetracyanonickelate is dissolved in the 50mL water, 0.05mol zinc hydroxide and 1: 1 mixture of zinc chloride mol ratio are dissolved in 50mL water and the 150mL glyme mixed solution.Under vigorous stirring, 50 ℃ slowly splash into potassium tetracyanonickelate solution in 1: 1 mixture solution of zinc hydroxide and zinc chloride mol ratio, generate that post precipitation continues vigorous stirring so that part glyme and the abundant complexing of precipitation.Filtering separation precipitation afterwards, the gained precipitation is changed slurry again with the mixed solution of 1: 3 glyme and water, and repeated centrifugation and change are washed and starched and are washed repeatedly, and increase the ratio to 3 of glyme/water in the washings one by one: 1.At last, till centrifugate can not detect potassium ion with potassium reagent.Dry 10h obtains the Zn/Ni DMC catalysts in 40 ℃ the vacuum drying oven with being deposited in.Its structural formula is (Zn)
2.04[Ni (CN)
6.08] Cl
0.12L
0.83(OH)
2.3(H
2O)
0.45X-ray diffraction records its degree of crystallinity more than 70%.
The organic ligand glyme can be substituted by other alcohol or ethers or organophosphorus compound in the present embodiment, preferred surrogate comprises Virahol, propyl carbinol, isopropylcarbinol, ethylene glycol, glycerine, glycol ether, glyme, diglyme, ethylene glycol monomethyl ether, ethylene glycol ethyl ether.
Following examples relate to the synthetic of aliphatic polycarbonate of the present invention.
The Zn/Co double metal cyanide ((Zn) that 10mg the foregoing description 1 is obtained
2.82[Co (CN)
7.38] Cl
0.49L
1.32(OH)
2.27(H
2O)
0.04) put into the 130mL autoclave, vacuumize drying, under nitrogen protection, add the oxyethane of 10 grams with syringe; charge into carbonic acid gas then to 10MPa, react 40h down, be cooled to room temperature rapidly at 80 ℃; slowly emit remaining carbon dioxide, take out product.Product is used methanol extraction after dissolving with trichloromethane again, and 70 ℃ of vacuum-dryings are counted output to constant weight, and product weighs 15 grams, and converting its catalytic efficiency is 1500 gram polymkeric substance/gram catalyzer, and it is 24500 that GPC measures its molecular weight.The product that obtains is the polymerized thylene carbonate ethyl ester, its IR collection of illustrative plates as shown in Figure 2,
1HNMR as shown in Figure 3, molecular structure is as follows:
Wherein, m=0.53, n=0.47.
The Zn/Co double metal cyanide ((Zn) that 20mg the foregoing description 1 is obtained
2.82[Co (CN)
7.38] Cl
0.49L
1.32(OH)
2.27(H
2O)
0.04) put into the 130mL autoclave, vacuumize drying, under nitrogen protection, add the propylene oxide of 10 grams with syringe; charge into carbonic acid gas then to 5MPa, react 5h down, be cooled to room temperature rapidly at 120 ℃; slowly emit remaining carbon dioxide, take out product.Product is used methanol extraction after dissolving with trichloromethane again, and 70 ℃ of vacuum-dryings are counted output to constant weight, and product weighs 15 grams, and converting its catalytic efficiency is 750 gram polymkeric substance/gram catalyzer, and it is 11000 that GPC measures its molecular weight.The product that obtains is a poly (propylene carbonate), and molecular structure is as follows:
Wherein, m=0.75, n=0.25.
The Zn-Co double metal cyanide ((Zn) that 3mg the foregoing description 1 is obtained
2.82[Co (CN)
7.38] Cl
0.49L
1.32(OH)
2.27(H
2O)
0.04) put into the 130mL autoclave, vacuumize drying, under nitrogen protection, add the propylene oxide of 20 grams with syringe; charge into carbonic acid gas then to 5MPa, react 24h down, be cooled to room temperature rapidly at 100 ℃; slowly emit remaining carbon dioxide, take out product.Product is used methanol extraction after dissolving with trichloromethane again, and 70 ℃ of vacuum-dryings are counted output to constant weight.Product weighs 25 grams, and converting its catalytic efficiency is 8333 gram polymkeric substance/gram catalyzer, and it is 55000 that GPC measures its molecular weight.The product that obtains is a poly (propylene carbonate), and molecular structure as shown in Figure 5
Wherein, m=0.47, n=0.53.
The Zn-Co DMC catalysts ((Zn) that 10mg the foregoing description 1 is obtained
2.82[Co (CN)
7.38] Cl
0.49L
1.32(OH)
2.27(H
2O)
0.04) put into the 130mL autoclave, vacuumize drying, under nitrogen protection, add the Styrene oxide 98min. of 10 grams with syringe; charge into carbonic acid gas then to 8MPa, react 12h down, be cooled to room temperature rapidly at 60 ℃; slowly emit remaining carbon dioxide, take out product.Product is used methanol extraction after dissolving with trichloromethane again, and 70 ℃ of vacuum-dryings are counted output to constant weight, and product weighs 12.5 grams, and converting its catalytic efficiency is 1250 gram polymkeric substance/gram catalyzer, and it is 12000 that GPC measures its molecular weight.Products therefrom is the polymerized thylene carbonate phenethyl ester, and molecular structure is as follows:
Wherein, m=0.94, n=0.06.
The Zn Co DMC catalysts ((Zn) that 3mg the foregoing description 1 is obtained
2.82[Co (CN)
7.38] Cl
0.49L
1.32(OH)
2.27(H
2O)
0.04) put into the 130mL autoclave, vacuumize drying, under nitrogen protection, add the cyclohexene oxide of 20 grams with syringe; charge into carbonic acid gas then to 5MPa; react 24h down at 120 ℃, add the cyclohexene oxides of 20 grams again, charge into carbonic acid gas then to 5MPa; react 24h down at 120 ℃; add the cyclohexene oxide of 20 grams again, charge into carbonic acid gas then, be cooled to room temperature rapidly to 5MPa; slowly emit remaining carbon dioxide, take out product.Product is used methanol extraction after dissolving with trichloromethane again, and 70 ℃ of vacuum-dryings are counted output to constant weight, and product weighs 66 grams, and converting its catalytic efficiency is 22000 gram polymkeric substance/gram catalyzer, and it is 97000 that GPC measures its molecular weight.Products therefrom is the polymerized thylene carbonate cyclohexyl, and molecular structure is as follows:
Wherein, m=0.60, n=0.40
Embodiment 9
The Zn Co DMC catalysts ((Zn) that 3mg the foregoing description 1 is obtained
2.82[Co (CN)
7.38] Cl
0.49L
1.32(OH)
2.27(H
2O)
0.04) put into the 130mL autoclave, vacuumize drying, under nitrogen protection, add the cyclohexene oxide of 10 grams with syringe; charge into carbonic acid gas then to 0.5MPa, react 200h down, be cooled to room temperature rapidly at 100 ℃; slowly emit remaining carbon dioxide, take out product.Product is used methanol extraction after dissolving with trichloromethane again, and 70 ℃ of vacuum-dryings are counted output to constant weight, and product weighs 10 grams, and converting its catalytic efficiency is 3300 gram polymkeric substance/gram catalyzer, and it is 59000 that GPC measures its molecular weight.Products therefrom is the polymerized thylene carbonate cyclohexyl, and molecular structure as shown in Figure 7.
Wherein, m=0.38, n=0.62.
The Zn Fe DMC catalysts ((Zn) that 10mg the foregoing description 2 is obtained
1.96[Fe (CN)
5.66] Cl
0.09L
0.9(OH)
0.34(H
2O)
1.63) put into the 130mL autoclave, vacuumize drying, under nitrogen protection, add the epoxy chloropropane of 10 grams with syringe; charge into carbonic acid gas then to 2MPa, react 24h down, be cooled to room temperature rapidly at 80 ℃; slowly emit remaining carbon dioxide, take out product.Product is used methanol extraction after dissolving with trichloromethane again, and 70 ℃ of vacuum-dryings are counted output to constant weight, and product weighs 10.3 grams, and converting its catalytic efficiency is 1030 gram polymkeric substance/gram catalyzer, and it is 13600 that GPC measures its molecular weight.Products therefrom is a polymerized thylene carbonate chlorine propyl ester, and molecular structure as shown in Figure 8.
Wherein, m=0.54, n=0.46.
Embodiment 11
The Zn Ni DMC catalysts ((Zn) that 10mg the foregoing description 3 is obtained
2.04[Ni (CN)
6.08] Cl
0.12L
0.83(OH)
2.3(H
2O)
0.45) put into the 130mL autoclave, vacuumize drying, under nitrogen protection, add the cyclohexene oxide of 8 grams and the butylene oxide ring of 8 grams with syringe; charge into carbonic acid gas then to 4MPa, react 24h down, be cooled to room temperature rapidly at 80 ℃; slowly emit remaining carbon dioxide, take out product.Product is used methanol extraction after dissolving with trichloromethane again, and 70 ℃ of vacuum-dryings are counted output to constant weight, and product weighs 14 grams, and converting its catalytic efficiency is 1400 gram polymkeric substance/gram catalyzer, and it is 23500 that GPC measures its molecular weight.Products therefrom is the inferior cyclohexyl of polymerized thylene carbonate butyl ester, and molecular structure is as follows.
Wherein, m=0.43, n=0.20; O=0.24, p=0.13.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the synthetic method of an aliphatic polycarbonate is characterized in that: be with DMC catalysts, carbonic acid gas and the epoxide autoclave of packing into, stir that catalyzed reaction is carried out in heating, obtains multipolymer;
Described double metal cyanide characterizes apparent degree of crystallinity 〉=70% that obtains with X-ray powder diffraction.
2. the synthetic method of aliphatic polycarbonate according to claim 1, it is characterized in that: the temperature of described catalyzed reaction is 60～120 ℃, and the reaction times is 5～200h; The weight ratio of described DMC catalysts and epoxide is between 1:500～20000; The pressure of described carbonic acid gas is at 0.5～10MPa.
3. the synthetic method of aliphatic polycarbonate according to claim 2, it is characterized in that: the pressure of described carbonic acid gas is 2～5MPa.
4. the synthetic method of aliphatic polycarbonate according to claim 1 and 2 is characterized in that: described epoxide is at least a in oxyethane, propylene oxide, epoxy chloropropane, butylene oxide ring, cyclohexene oxide and the Styrene oxide 98min..
5. the synthetic method of aliphatic polycarbonate according to claim 1, it is characterized in that: described DMC catalysts is prepared by following method: soluble metal M1 halogenide or itself and the mixture of M1 oxide compound or M1 oxyhydroxide and the cyanide complex of another kind of soluble metal M2 are reacted in the mixed solvent of water or organic ligand and water, the precipitation that obtains is the mixed solvent washing of water or organic ligand and water again, obtain solid with centrifugal or filtering method, vacuum-drying obtains DMC catalysts again;
Described M1 and M2 are Al, Zn, and Co, Fe, Ni, Mn, Mo, V or Cu, wherein the mol ratio of M1/M2 is 1.5-4;
Described organic ligand is alcohol, mercaptan, phenol, ether, imines or organo phosphorous compounds.
6. the synthetic method of aliphatic polycarbonate according to claim 5, it is characterized in that: described DMC catalysts is prepared by following method: the cyanide complex of the soluble metal M2 solution A that forms soluble in water, the mixture of soluble metal M1 halogenide or itself and M1 oxide compound or M1 oxyhydroxide is dissolved in the mixed solvent of organic ligand and water and forms solution or suspension liquid B, wherein the volume ratio of organic ligand and water is 3: 1-1: 3; B splashed among the A react, temperature of reaction is 20-50 ℃; The precipitation that obtains is the mixed solvent washing of water or organic ligand and water again, and wherein the volume ratio of organic ligand and water is 3: 1-1: 3, obtain solid with centrifugal or filtering method, and obtain DMC catalysts in 20-50 ℃ of vacuum-drying again.
7. according to the synthetic method of claim 5 or 6 described aliphatic polycarbonates, it is characterized in that: described M1 is Zn; Described M2 is Co, Ni or Fe.
8. according to the synthetic method of claim 5 or 6 described aliphatic polycarbonates, it is characterized in that: described organic ligand is Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, ethylene glycol, glycerine, glyme, diglyme, ethylene glycol monomethyl ether or ethylene glycol ethyl ether.
9. the synthetic method of aliphatic polycarbonate according to claim 8, it is characterized in that: described organic ligand is the trimethyl carbinol or glyme.
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| CN102179262B (en) * | 2011-03-28 | 2016-05-11 | 河北工业大学 | A kind of preparation method of double metal cyanide catalyst for polycarbonate synthesis |
| CN102206333B (en) * | 2011-04-18 | 2013-12-04 | 中科院广州化学有限公司 | Low molecular weight polycarbonate polyatomic alcohol and preparation method and application thereof |
| CN103102481B (en) * | 2013-01-28 | 2015-02-18 | 浙江大学 | Synthesis method of aliphatic polycarbonate with regular chain structure |
| KR102220786B1 (en) * | 2013-07-18 | 2021-03-02 | 에스케이이노베이션 주식회사 | Double Metal Cyanide Catalyst and Epoxide/Carbon Dioxide Copolymer |
| CN104927040B (en) * | 2014-03-17 | 2016-09-07 | 中国石油化工股份有限公司 | The preparation method of the fatty poly-ester carbonate of dmc catalyst catalysis |
| CN104987502B (en) * | 2015-07-24 | 2017-04-19 | 中国科学院长春应用化学研究所 | Co-precipitation double metal cyanide catalyst, and preparation method and application thereof |
| CN105504257B (en) * | 2015-12-28 | 2018-04-06 | 广东工业大学 | A kind of preparation method of the chloride poly (propylene carbonate) polyalcohol of side chain |
| CN113546667B (en) * | 2021-07-01 | 2023-08-08 | 佛山科学技术学院 | Double metal cyanide catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1228039A (en) * | 1996-10-16 | 1999-09-08 | 阿科化学技术公司 | Double metal cyanide catalysts containing functionalized polymers |
| CN1692135A (en) * | 2002-06-20 | 2005-11-02 | Posco公司 | Method of preparing catalyst for polymerization of aliphatic polycarbonate and method of polymerizing aliphatic polycarbonate using same |
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| CN1228039A (en) * | 1996-10-16 | 1999-09-08 | 阿科化学技术公司 | Double metal cyanide catalysts containing functionalized polymers |
| CN1692135A (en) * | 2002-06-20 | 2005-11-02 | Posco公司 | Method of preparing catalyst for polymerization of aliphatic polycarbonate and method of polymerizing aliphatic polycarbonate using same |
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