CN103626986A - Novel preparation method of magnetic bimetallic cyanide complex catalyst - Google Patents
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Abstract
本发明解决所述催化剂技术问题的技术方案是，设计一种磁性双金属氰化物络合催化剂，该催化剂为在有机配体存在下，由过量ZnCl2、一定比例的Fe2+和Fe3+与K3Fe(CN)6在水中反应，生成的沉淀物经过滤、化浆、真空干燥而制备的。其特征在于：获得高度分散性的非晶态磁性双金属氰化物。这种非晶态的磁性双金属氰化物催化活性高，反应速度快，其催化性能明显优于利用传统制备方法制备的磁性双金属氰化物，且易于与聚醚产物分离，可以回收利用。该制备方法包括：1.磁性双金属氰化物前躯体的制备；2.磁性双金属氰化物的制备。该催化剂制备方法工艺简单，不需要或者只需少量的设备改造就可实现工业化生产，成本低，适应性好，便于实际推广应用。
The technical solution of the present invention to solve the technical problem of the catalyst is to design a magnetic double metal cyanide complex catalyst, which is composed of excess ZnCl 2 , a certain proportion of Fe 2+ and Fe 3+ in the presence of organic ligands. It is prepared by reacting with K 3 Fe(CN) 6 in water, and the resulting precipitate is filtered, pulped and dried in vacuum. It is characterized in that it obtains highly dispersed amorphous magnetic double metal cyanide. The amorphous magnetic double metal cyanide has high catalytic activity and fast reaction speed, its catalytic performance is obviously better than that of the magnetic double metal cyanide prepared by traditional preparation methods, and it is easy to separate from polyether products and can be recycled. The preparation method comprises: 1. preparation of magnetic double metal cyanide precursor; 2. preparation of magnetic double metal cyanide. The preparation method of the catalyst is simple in process, can realize industrialized production without or only a small amount of equipment modification, has low cost, good adaptability, and is convenient for practical popularization and application.
Description
Technical field
The present invention relates to catalyst technology, be specially synthetic middle magnetic bimetallic cyanide complex catalyst using of nonionogenic tenside of a kind of high molecular and narrow distribution and preparation method thereof.
Background technology
In tensio-active agent field, take fatty alcohol as initiator, the nonionogenic tenside (conventionally referred to as polyethers) that oxyethane, propylene oxide or its mixture be chain propagation agent synthesized of take is to apply in recent years fine chemical product more and more widely.Narrow molecular weight distributions and high molecular weight polyether have the stable feature of capability and performance, and the synthetic as above polyethers of advantage of wish, the selection of catalyzer and preparation are crucial.The high-performance polyethers occurring is in the market made by double metal cyanide (DMC) complex catalyst.Compare with traditional epoxide catalyzer (as KOH), the polyether glycol of preparing as catalyzer with DMC has the advantages such as low-unsaturation-degree, low unit alcohol content, high molecule mass and narrow molecular weight distributions, and its functionality approaches theoretical value.
By the technological difficulties of DMC production high-performance poly ethoxylated polyhydric alcohol, be the preparation of catalyzer.Since the sixties, first AM General rubber for tire company applied for a patent, through 30 years of researches and exploitation, there is a series of patent about dmc catalyst.The common ground of these patents is: (1) is mainly Zn for the preparation of the DMC of catalyzer
3[Co (CN)
6]
2and Zn
3[Fe (CN)
6]
2; (2) be all with a kind of aqueous metal salt and the preparation of the another kind of metal cyanides aqueous solution; (3) all need to process DMC with organic ligand; (4) technique of Kaolinite Preparation of Catalyst need repeatedly precipitate and wash.
The catalytic activity of synthetic dmc catalyst is high in the market, the consumption in polyethers preparation seldom (5 * 10
-6～1000 * 10
-6), but also residual catalyzer must be removed from polyether products after polymerization, otherwise can cause that other side reactions occur, and affect storage and the application of polyethers.And magnetic dmc catalyst utilizes its transporting action under additional the action of a magnetic field, can realize residual catalyst is effectively removed from polyether products.Therefore the innovative development of novel magnetic catalyzer has very important practical significance.
Summary of the invention
For the deficiencies in the prior art, the main technical problem to be solved in the present invention is to develop a kind of novel magnetic bimetallic cyanide complex catalyst and preparation method thereof.This catalyzer has good narrow molecular weight distributions effect for the synthetic of polyether product, and molecular weight is generally thousands of several ten thousand.Be applicable to traditional autoclave or intermittent type polyether product production technique, catalytic rate is higher than traditional catalyst, and the catalyzer after having reacted is easy to separation, can recycle; This method for preparing catalyst technique is simple, does not need or only needs a small amount of scrap build just can realize suitability for industrialized production, and cost is low, and adaptability is good, is convenient to actual applying.
The technical scheme that the present invention solves described catalyst technology problem is, designs a kind of magnetic bimetallic cyanide complex catalyst, and this catalyzer is under organic ligand exists, by ZnCl
2(excessive), Fe
2+and Fe
3+(certain proportion) and K
3fe (CN)
6in water, react, the throw out of generation after filtration, change slurry, prepared by vacuum-drying.It is characterized in that: the magnetic amorphous DMC that obtains high dispersion.This amorphous magnetic DMC catalytic activity is high, and speed of response is fast, and its catalytic performance is obviously better than the DMC that utilizes traditional preparation method to prepare, and is easy to separatedly with polyether products, can recycle.
The technical scheme that the present invention solves described preparation method's technical problem is, designs a kind of preparation method of magnetic double metal cyanide (DMC) complex catalyst of the polyether product for the synthesis of high molecular and narrow distribution, and this preparation method comprises:
1. the preparation of magnetic double metal cyanide (DMC) precursor.The ZnCl that preparation massfraction is 30-50%
2the K of (solution A) and 10-30%
3fe (CN)
6the aqueous solution (solution B); Preparation contains 10-40%Fe
2+the aqueous solution (solution C); Preparation contains 10-40%Fe
3+the aqueous solution (solution D); Prepare after above-mentioned solution, solution B, solution C, solution D are dropwise joined in the solution A of 10-100ml and the mixed solution of organic ligand according to the rate of addition of 0.1-10ml/min simultaneously, wherein the Zn in mixed solution
2+: Fe
3+: Fe
2+the mass ratio that feeds intake be controlled between 1-10:0.1-3:0.01-2, the volume ratio of described solution A and organic ligand is controlled between 10-1:1-10, temperature of reaction is controlled at 20-50 ℃, rate of addition is 0.1-10ml/min, control rotating speed at 1000-10000r/min, stirring reaction 10-100min, obtains precursor slurries.Synthetic method of the present invention has been reformed the preparation process (only divalent metal salt solution being joined to the aqueous solution that then adds organic ligand in metal cyanides salts solution) of conventional DMC, controls the addition sequence of raw material, and adds a certain proportion of Fe
2+, Fe
3+the aqueous solution, optimized relevant ions concentration proportioning, the catalyzer of gained is essentially amorphous, catalyst activity is also higher, speed of response is fast, and easily separated with polyether products.Described ferrous ion, from ferrous salt, comprises the solubility salts such as Iron nitrate, iron protochloride, ferrous sulfate, ferrous phosphate and ferrous perchlorate; Iron ion is from solubility salts such as iron nitrate, iron(ic) chloride, ferric sulfate, tertiary iron phosphate and Iron triperchlorates; Described organic ligand is from organic ligands such as glycol dimethyl ether, ethylene glycol diethyl ether, the trimethyl carbinol and Isosorbide-5-Nitrae-dioxane.
2. the preparation of magnetic double metal cyanide (DMC): by resulting precursor slurries filtration under diminished pressure, use again mixed liquefied slurry, the filtration of organic ligand and redistilled water (volume ratio 1-10:1), repeat this operation 3 times, finally with pure organic ligandization slurry, filtration, finally at 50-100 ℃, dry, obtain magnetic double metal cyanide (DMC) complex catalyst.
The present invention is by aforesaid method, and on the synthetic basis of conventional dmc catalyst, (conventional dmc catalyst is synthetic is under the existence at organic ligand, metal-salt ZnCl
2with metal cyanides Zn
3[Co (CN)
6]
2or Zn
3[Fe (CN)
6]
2in the aqueous solution reaction and preparation.), adopt efficient organic ligand (suitable organic ligand is water miscible fatty alcohol, as ethanol, b propanol, propyl carbinol, isopropylcarbinol, 2-butanols and the trimethyl carbinol), by Fe
2+and Fe
3+with certain proportion, join in reaction mixture. prepared novel magnetic double metal cyanide (DMC) catalyzer.Compare with existing catalysis technique, the dmc catalyst of the amorphous state that the present invention is synthetic is compared with conventional dmc catalyst, there is higher catalytic activity, and can be activated quickly, improved residual catalyst after the catalytic activity of catalyzer and reaction complete and be easy to from polyether products separatedly, can recycle.Catalyzer of the present invention is applicable to traditional autoclave or intermittent type polyether product production technique, there is catalysis speed fast (with respect to traditional catalyst KOH or NaOH), the feature of the high and narrowly distributing of catalyzed reaction molecular weight product, and owing to introducing moulding process, making the catalyzer after having reacted is the advantage of recoverable through simple process, reduce use cost, there is good economy and the feature of environmental protection.Because technique is simple, do not need or only need a small amount of scrap build just can realize suitability for industrialized production simultaneously, cost is low, and adaptability is good, is convenient to actual applying.
Accompanying drawing explanation
Fig. 1 be of the present invention and bimetallic cyanide complex Isosorbide-5-Nitrae-dioxane shaping of catalyst after TEM figure.
Embodiment:
Below in conjunction with embodiment and accompanying drawing thereof, further narrate the present invention.
Magnetic double metal cyanide (DMC) complex catalyst of the present invention's design adopts coprecipitation method by Fe
2+, Fe
3+be added drop-wise to Zn
2+in the solution of organic ligand, processization slurry, filters, and the processes such as oven dry finally make:
1. the preparation of magnetic double metal cyanide (DMC) precursor.The ZnCl that preparation massfraction is 30-50%
2the K of (solution A) and 10-30%
3fe (CN)
6the aqueous solution (solution B); Preparation contains 10-40%Fe
2+the aqueous solution (solution C); Preparation contains 10-40%Fe
3+the aqueous solution (solution D); Prepare after above-mentioned solution, solution B, solution C, solution D are dropwise joined in the solution A of 10-100ml and the mixed solution of organic ligand according to the rate of addition of 0.1-10ml/min simultaneously, wherein the Zn in mixed solution
2+: Fe
3+: Fe
2+the mass ratio that feeds intake be controlled between 1-10:0.1-2:0.01-1, the volume ratio of described solution A and organic ligand is controlled between 10-1:1-10, temperature of reaction is controlled at 20-50 ℃, rate of addition is 0.1-10ml/min, rotating speed is controlled at 1000-10000r/min, stirring reaction 10-100min, obtains precursor slurries
Described ferrous ion, from ferrous salt, comprises the solubility salts such as Iron nitrate, iron protochloride, ferrous sulfate, ferrous phosphate and ferrous perchlorate; Iron ion is from solubility salts such as iron nitrate, iron(ic) chloride, ferric sulfate, tertiary iron phosphate and Iron triperchlorates; Described organic ligand is from organic ligands such as glycol dimethyl ether, ethylene glycol diethyl ether, the trimethyl carbinol and Isosorbide-5-Nitrae-dioxane.
2. the preparation of magnetic double metal cyanide (DMC): by resulting precursor slurries filtration under diminished pressure, use again mixed liquefied slurry, the filtration of organic ligand and redistilled water (volume ratio 1-10:1), repeat this operation 3 times, finally with pure organic ligandization slurry, filtration, finally at 50-100 ℃, dry, obtain magnetic double metal cyanide (DMC) complex catalyst.
Magnetic double metal cyanide (DMC) after described oven dry can be block solid of being of yellow, safran, khaki color or light brown.
In the preparation process of catalyzer involved in the present invention, redox reaction does not occur, organic ligand is and Zn
2+coordination, this ligand has been destroyed Zn
3[Fe (CN)
6]
212H
2the crystalline structure of O.Organic ligand and Zn
2+after coordination, Zn
2+in catalyst surface enrichment, the Cl in catalyzer
-play charge neutrality effect.Active structure in dmc catalyst and with the Zn of oxygen coordination
2+relevant, the ligancy of oxygen and zinc is higher, and the activity of catalyzer is better.Fe
3+in dmc catalyst, played this activation of effect of activation Zn-N key by Fe
3+the strong interaction of p-CN causes.
It is that the polyethers of initiator is synthetic that catalyzer involved in the present invention is applicable to catalysis fatty alcohol, related alcohol can be low-molecular-weight methyl alcohol, ethanol, glycerol, also can be the higher alcohols of higher molecular weight, such as hexadecanol, oleyl alcohol, stearyl alcohol, lauryl alcohol etc.; Also the polyethers that is applicable to catalysis lipid acid and is initiator is synthetic, and related acid can be low-molecular-weight propionic acid, butyric acid, hexanodioic acid etc., can be also the higher fatty acid of higher molecular weight, such as stearic acid, oleic acid etc.
Catalyzer involved in the present invention is applicable to the ring-opening polymerization of catalytic epoxyethane, the ring-opening polymerization of catalysis propylene oxide, the reactions such as catalytic epoxyethane and propylene oxide copolymerization or block polymerization.The pfpe molecule weight range catalyzing and synthesizing is the product of the big or middle molecular weight between 1000-20000.
Narrow molecular weight distributions index calculation method involved in the present invention is prior art, but slightly change (with reference to Mt．Mountain Wen Xiong etc., the detection of tlc to molecular weight distribution, polymkeric substance magazine, 1,518-523,1970.Fumio Kamiyama et al.Determination of Molecular Weight Distribution of Polymeric Substances by Thin-Layer Chromatography, Polymer Journal, 1,518-523,1970; ; Cross Bian Wuhong etc., thin-layer chromatography and the sign of matrix laser desorption ionization mass spectra to polyether mixture, mass spectrum communication, 21,787-791,2007.Takehiro Watanabe et al.Characterization of polyether mixtures using thin-layer chromatography and matrix-assisted laser desorption/ionization mass spectrometry, Rapid Communications in Mass Spectrometry, 21,787-791,2007).First EO (oxyethane) adduct number (can be regarded as and have different molecular weight) of supposing synthetic target product is n, by above-mentioned catalyst synthesizing polyether, the product obtaining adopts tlc to launch (with reference to accompanying drawing 1) with corresponding developping agent, then with contain the standard model that adduct number is n EO (can buy from SigmaAldrich or Nippon Kasei Chemical Company) and contrast, the spot with identical relative retention time value (Rf) can be considered as having identical EO adduct number (referring to Fig. 1), the spot that has an identical Rf value with standard model can be considered as having the product of n EO adduct number, then determine and there is n+1 successively, n+2, n-1, the position of the product of n-2 EO adduct number, then carry out thin layer scanning, determine the area of each spot, by calculating the area of spot, recently calculate EO dispersion index, method of calculation reference equation formula 1.
I in equation 1 is integer, A-speck area.
According to equation 1, calculate, the narrow distribution range of molecular weight of magnetic double metal cyanide of the present invention (DMC) catalyst reaction gained polyether product is 75-100%, can reach 100%, than the 30-40% of traditional KOH or NaOH catalyzer, increase exponentially.
The present invention does not address part and is applicable to prior art.
Below specific embodiments of the invention.Described embodiment is only for specifically describing the present invention, rather than limits claim of the present invention.
Carry out the preparation of magnetic double metal cyanide (DMC) precursor.The ZnCl that preparation massfraction is 40%
2(solution A) and 20% K
3fe (CN)
6the aqueous solution (solution B); Preparation contains 20%FeCl
2the aqueous solution (solution C) and 20%FeCl
3the aqueous solution (solution D); Prepare after above-mentioned solution, the mixed solution of solution B and the trimethyl carbinol, solution C, solution D are dropwise joined in the solution A of 30ml according to the rate of addition of 2ml/min simultaneously, wherein the Zn in mixed solution
2+: Fe
3+: Fe
2+the mass ratio that feeds intake be controlled at 10:2:1, the volume ratio of described solution A and the trimethyl carbinol is controlled at 5:1, temperature of reaction is controlled at 30 ℃, rotating speed is controlled at 3000r/min, stirring reaction 40min obtains precursor slurries.
By resulting precursor slurries filtration under diminished pressure, use again mixed liquefied slurry, the filtration of organic ligand and redistilled water (volume ratio 3:1), repeat this operation 3 times, finally with pure organic ligandization slurry, filtration, finally at 60 ℃, dry, obtain magnetic double metal cyanide (DMC) complex catalyst.
Magnetic double metal cyanide (DMC) catalyzer of the present embodiment is khaki color; After testing, catalytic is 3.4gEO/min, and narrow distribution coefficient is 100%.
Embodiment 2
Carry out the preparation of magnetic double metal cyanide (DMC) precursor.The ZnCl that preparation massfraction is 40%
2(solution A) and 20% K
3fe (CN)
6the aqueous solution (solution B); Preparation contains 20%FeCl
2the aqueous solution (solution C); Preparation contains 20%FeCl
3the aqueous solution (solution D); Prepare after above-mentioned solution, by the solution A of 25ml, and the mixed solution of solution C and solution D dropwise joins in the mixed solution of solution B and the trimethyl carbinol according to the rate of addition of 3ml/min simultaneously, wherein the Zn in mixed solution
2+: Fe
3+: Fe
2+the mass ratio that feeds intake be controlled between 10:2:1, the volume ratio of described solution A and the trimethyl carbinol is controlled between 5:1, temperature of reaction is controlled at 30 ℃, rotating speed is controlled at 3000r/min, stirring reaction 40min obtains precursor slurries
The preparation of magnetic double metal cyanide (DMC): by resulting precursor slurries filtration under diminished pressure, use again mixed liquefied slurry, the filtration of organic ligand and redistilled water (volume ratio 5:1), repeat this operation 3 times, finally with pure organic ligandization slurry, filtration, finally at 60 ℃, dry, obtain magnetic double metal cyanide (DMC) complex catalyst.
Magnetic double metal cyanide (DMC) catalyzer of the present embodiment is safran; After testing, catalytic is 1.6gEO/min, and narrow distribution coefficient is 90%.
Embodiment 3
Carry out the preparation of magnetic double metal cyanide (DMC) precursor.The ZnCl that preparation massfraction is 30%
2(solution A) and 15% K
3fe (CN)
6the aqueous solution (solution B); Preparation contains 20%FeSO
4the aqueous solution (solution C); Preparation contains 20%Fe (SO
4)
3the aqueous solution (solution D); Prepare after above-mentioned solution, the mixed solution of solution B, C and solution D is dropwise joined in the solution A of 40ml and the mixed solution of Isosorbide-5-Nitrae-dioxane according to the rate of addition of 1ml/min, wherein the Zn in mixed solution
2+: Fe
3+: Fe
2+the mass ratio that feeds intake be controlled between 15:3:2, the volume ratio of described solution A and Isosorbide-5-Nitrae-dioxane is controlled between 5:1, temperature of reaction is controlled at 40 ℃, rotating speed is controlled at 5000r/min, stirring reaction 30min obtains precursor slurries
The preparation of magnetic double metal cyanide (DMC): by resulting precursor slurries filtration under diminished pressure, use again mixed liquefied slurry, the filtration of organic ligand and redistilled water (volume ratio 5:1), repeat this operation 3 times, finally with pure organic ligandization slurry, filtration, finally at 70 ℃, dry, obtain magnetic double metal cyanide (DMC) complex catalyst.
Magnetic double metal cyanide (DMC) catalyzer is yellow, and catalytic is 1.3g EO/min, and narrow distribution coefficient is 90%.
Carry out the preparation of magnetic double metal cyanide (DMC) precursor.The ZnCl that preparation massfraction is 30%
2(solution A) and 15% K
3fe (CN)
6the aqueous solution (solution B); Preparation contains 15%Fe (NO
3)
2the aqueous solution (solution C); Preparation contains 30%Fe (NO
3)
3the aqueous solution (solution D); Prepare after above-mentioned solution, by 5ml1, the mixing solutions of the mixing solutions of 4-dioxane solution and solution A and solution C and solution D dropwise joins solution B and 5ml1 according to the rate of addition of 1ml/min simultaneously, in the mixed solution of 4-dioxane solution, and the Zn in mixed solution wherein
2+: Fe
3+: Fe
2+the mass ratio that feeds intake be controlled between 10:1:1, the volume ratio of described solution A and Isosorbide-5-Nitrae-dioxane is controlled between 5:1, temperature of reaction is controlled at 40 ℃, rotating speed is controlled at 7000r/min, stirring reaction 20min obtains precursor slurries.
The preparation of magnetic double metal cyanide (DMC): by resulting precursor slurries filtration under diminished pressure, use again mixed liquefied slurry, the filtration of organic ligand and redistilled water (volume ratio 3:1), repeat this operation 3 times, finally with pure organic ligandization slurry, filtration, finally at 70 ℃, dry, obtain magnetic double metal cyanide (DMC) complex catalyst.
Magnetic double metal cyanide (DMC) catalyzer is brown color, and catalytic is 1.9g EO/min, and narrow distribution coefficient is 75%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910865A (en) * | 2014-03-27 | 2014-07-09 | 上海应用技术学院 | Bimetallic cyanide catalyst containing micro-molecular polyether polyol and preparation method of bimetallic cyanide catalyst |
| CN106041117A (en) * | 2016-05-27 | 2016-10-26 | 浙江工业大学 | Preparation method of nanoscale magnetic Fe 3O 4 stabilized bimetal zero-valent iron |
| CN114058003A (en) * | 2021-12-06 | 2022-02-18 | 中国科学院长春应用化学研究所 | A kind of double metal cyanide catalyst for easy separation and preparation method thereof |
| CN114203982A (en) * | 2021-11-01 | 2022-03-18 | 江苏大学 | A kind of preparation method of vanadium-based Prussian blue analog/carbon nanotube composite material and its application in the cathode of aqueous zinc ion battery |
| CN115785435B (en) * | 2022-12-29 | 2023-08-11 | 杭州普力材料科技有限公司 | Method for preparing polyether polyol by one-step method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910865A (en) * | 2014-03-27 | 2014-07-09 | 上海应用技术学院 | Bimetallic cyanide catalyst containing micro-molecular polyether polyol and preparation method of bimetallic cyanide catalyst |
| CN103910865B (en) * | 2014-03-27 | 2017-02-01 | 上海应用技术学院 | Bimetallic cyanide catalyst containing micro-molecular polyether polyol and preparation method of bimetallic cyanide catalyst |
| CN106041117A (en) * | 2016-05-27 | 2016-10-26 | 浙江工业大学 | Preparation method of nanoscale magnetic Fe 3O 4 stabilized bimetal zero-valent iron |
| CN114203982A (en) * | 2021-11-01 | 2022-03-18 | 江苏大学 | A kind of preparation method of vanadium-based Prussian blue analog/carbon nanotube composite material and its application in the cathode of aqueous zinc ion battery |
| CN114203982B (en) * | 2021-11-01 | 2023-03-24 | 江苏大学 | Preparation method of vanadium-based Prussian blue analogue/carbon nanotube composite material and application of vanadium-based Prussian blue analogue/carbon nanotube composite material to water-based zinc ion battery anode |
| CN114058003A (en) * | 2021-12-06 | 2022-02-18 | 中国科学院长春应用化学研究所 | A kind of double metal cyanide catalyst for easy separation and preparation method thereof |
| CN115785435B (en) * | 2022-12-29 | 2023-08-11 | 杭州普力材料科技有限公司 | Method for preparing polyether polyol by one-step method |
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