CN1080590C - Double metal cyanide catalyst and its prepn. method - Google Patents
Double metal cyanide catalyst and its prepn. method Download PDFInfo
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- CN1080590C CN1080590C CN98108166A CN98108166A CN1080590C CN 1080590 C CN1080590 C CN 1080590C CN 98108166 A CN98108166 A CN 98108166A CN 98108166 A CN98108166 A CN 98108166A CN 1080590 C CN1080590 C CN 1080590C
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Abstract
The present invention relates to a double metal cyanide catalyst, which is composed of Zn3[Co(CN)6]2. aZnCl2. bH2O. cL. dL', wherein L is an organic alcohol, L' is one kind of organic ether, the mixture of the ester and the alcohol is used for processing the mixture of a zinc salt and hexacobaltocyanide to obtain precipitates which are washed and are dried in vacuum, and the catalyst is prepared. The DMC catalyst has the advantages of low use concentration and simple preparation method, and the DMC catalyst can be easily separated from polyether glycol and can synthesize unsaturated polyether glycol within a wide temperature range.
Description
The invention belongs to catalyst, relate in particular to a kind of DMC catalysts and preparation method thereof.
The application of bimetallic cyanide complex catalyst in epoxide polymerization is widely known by the people.The PPG synthetic with adopting KOH compared, and the DMC PPG with same molecular amount has lower degree of unsaturation.Because PPG is the intermediate of synthesis of polyurethane, the height of PPG degree of unsaturation directly influences the performance of polyurethane product, therefore the DMC PPG has the wide development potentiality in polyurethane field, along with the raising of people to the polyurethane product performance requirement, developing high performance DMC catalysts has become a hot subject in the polyurethane research field.
The DMC compound is meant to have (CN) b (A) c of Ma[M '] compound of d structure, wherein, M, M ' they are metal ions, A is CN
-Other part in addition, a, b, c, d are coefficients, b＞c.Discover some double metal cyanides through some treatment of organic matters of organic obtain can the polymerization of catalysis epoxidation thing dmc catalyst.After the sixties in this century, AM General rubber for tire company at first applied for a patent, the patent of a series of relevant dmc catalysts has appearred, as U.S.Pat 3,278,457. 3,278,458.3,404,109. 3,427,256. 3,829,505. 3,941,849. 5,482,908. Jan Pat4-145,123. Ep 0,761, the common ground of 708 these patents of A2. is: the DMC compound that (1) is used to prepare dmc catalyst mainly is six ferricyanic acid zinc (Zn
3[Fe (CN)
6]
2), zinc hexacyanocobaltate (Zn
3[Co (CN)
6]
2Because six ferricyanic acid zinc are yellow, are replaced by zinc hexacyanocobaltate, patent in recent years all adopts zinc hexacyanocobaltate to prepare dmc catalyst; (2) the DMC compound all is with a kind of fortified aqueous of slaine and another kind of metal cyano complex salt weak solution prepared in reaction, zinc hexacyanocobaltate commonly used is by the weak solution prepared in reaction of the concentrated solution of zinc chloride and Cobalt Potassium Cyanide or hexacyanocobaltate acid calcium, react completely for making, it is excessive that zinc chloride needs.During preparation, can be added to liquor zinci chloridi in the hexacyanocobaltate acid potassium solution, also can be added to the hexacyanocobaltate acid potassium solution in the liquor zinci chloridi; (3) handle the DMC compound with organic ligand.Existing patent is general to adopt a kind of organic matter to handle the DMC compound, and for example U.S.Pat 3,404, and 109 handle the DMC compound with dioxane, acetone, glycol dimethyl ether respectively; U.S.Pat 3.427,256 handles the DMC compound with diethylene glycol diethyl ether, triethylene glycol diethyl ether, diethylene glycol dimethyl ether respectively; U.S.Pat 5.482,908 with molecular weight greater than DMC compound in 500 the polyether Glycols place; Jan.Pat 4-145,123 with tert-butyl alcohol processing DMC compound.
Treatment of organic matters of organic has a significant impact the performance of dmc catalyst, and the DMC compound of handling through organic matter does not have higher degree of crystallinity, generally is not less than 35%, and catalytic performance is relatively poor.The degree of crystallinity of the DMC compound of handling through organic matter has reduction in various degree, and its catalytic activity then has improving in various degree, the organic matter difference of employing, and the performance of dmc catalyst is also inequality.
The dmc catalyst of these inventions can dissolve or be scattered in the PPG with small particle well, is difficult to remove PPG outward appearance muddiness.
Goal of the invention of the present invention provides a kind of DMC catalysts that easily separates and preparation method thereof from product.
Catalyst of the present invention composed as follows:
Zn
3[Co(CN)
6]
2·aZnCl
2·bH
2O·cL·dL′
Wherein L is a kind of organic alcohol, and L ' is a kind of organic ether, and a, b, c, d are coefficients, a=0.05-1.0, b=1.0-2.0, c=0.5-3.0, d=1.0-4.0.
Aforesaid organic alcohol is the organic alcohol with C4-C10 of tertiary alcohol structure, is preferably the tert-butyl alcohol and tert-pentyl alcohol.
Aforesaid organic ether is the organic ether that contains 2-4 ether oxygens key, is preferably glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether.
Aforesaid Preparation of catalysts method is as follows:
A. the aqueous solution, alcohol, the ether of the hexacyanocobaltate acid salt of dense zinc salt solution, rare alkali metal or alkaline-earth metal are added in the reactor simultaneously, stir, generate precipitation, separate.Wherein the addition of material is:
Zn
2+: [Co (CN)
6]
3-=(2-5): 1 (mol ratio)
Alcohol: ether=(0.1-10): 1 (volume ratio)
Every mole of [Co (CN)
6]
3-Add organic matter 4-15 liter
B. isolated sediment use with (a) step in form the organic matter of isodose mutually and equal the mixture that organic matter adds 1/15～1/4 water of volume and carry out pulping and washing, isolate sediment,
C. the sediment after separating use again with (a) step in form mutually that the organic matter of isodose carries out pulping and washing, isolate sediment under 60 ℃ of temperature, vacuum drying obtains catalyst to constant weight.
Aforesaid zinc salt is an inorganic zinc salt.
Aforesaid zinc salt is zinc chloride, zinc bromide, zinc nitrate, zinc sulfate preferably.
Aforesaid hexacyanocobaltate acid salt is Cobalt Potassium Cyanide, hexacyanocobaltate acid sodium preferably.
The dmc catalyst of the present invention's preparation can be used to prepare random or block copolymer, having in the presence of the hydroxyl initiator, can prepare PPG.The epoxides that is used to prepare PPG is oxirane preferably, expoxy propane, epoxy butane, styrene oxide.
Dmc catalyst of the present invention has following advantage compared with prior art:
(1) dmc catalyst caking precipitating after reaction generates PPG is come out, and is easy to separate.
(2) degree of unsaturation of the PPG of dmc catalyst preparation is not higher than 0.007meq/g, the degree of unsaturation low 50% of the PPG that the dmc catalyst that provides than prior art prepares.
(3) dmc catalyst is under the working concentration that is not higher than 200ppm, and polymerization conversion is higher than 90%.
(4) catalyst can use in 0-200 ℃ temperature range.
(5) preparation method is simple.
Embodiment 1
A. the 5.1g Cobalt Potassium Cyanide is dissolved in the 100ml deionized water, makes 0.15mol/l hexacyanocobaltate acid potassium solution; The 10.0g zinc chloride is dissolved in the 20ml deionized water, makes the 3.67mol/l liquor zinci chloridi, stirring in the 180ml tert-butyl alcohol, 20ml glycol dimethyl ether, hexacyanocobaltate acid potassium solution, the liquor zinci chloridi adding reactor, generate precipitation simultaneously, separate; Wherein the addition of material is:
Zn
2+: [Co (CN)
6]
3-=4.9: 1 (mol ratio)
The tert-butyl alcohol: glycol dimethyl ether=9: 1 (volume ratio)
Every mole of [Co (CN)
6]
3-Add 13.3 liters of organic matters
B. isolated sediment is isolated sediment with the mixture pulping and washing of the 180ml tert-butyl alcohol and 20ml glycol dimethyl ether and 20ml water;
C. the sediment after separating is used the 180ml tert-butyl alcohol and 20ml glycol dimethyl ether pulping and washing again, and isolated sediment is under 60 ℃ of temperature, and vacuum drying obtains catalyst A to weight.The analysis showed that this catalyst has following composition: Zn
3[Co (CN)
6]
20.093ZnCl
22.7C
4H
10O1.2C
4H
10O
2
Embodiment 2
A. the 5.3g Cobalt Potassium Cyanide is dissolved in the 40ml deionized water, makes 0.4mol/l hexacyanocobaltate acid potassium solution; The 8.7g zinc chloride is dissolved in the 20ml deionized water, makes the 3.2mol/l liquor zinci chloridi, stirring in 60ml tert-pentyl alcohol, 10ml ethylene glycol diethyl ether, hexacyanocobaltate acid potassium solution, the liquor zinci chloridi adding reactor, generate precipitation simultaneously, separate; Wherein the addition of material is:
Zn
2+: [Co (CN)
6]
3-=4.0: 1 (mol ratio)
Tert-pentyl alcohol: ethylene glycol diethyl ether=6.0: 1 (volume ratio)
Every mole of [Co (CN)
6]
3-Add 4.4 liters of organic matters
B. isolated sediment is isolated sediment with the mixture pulping and washing of 60ml tert-pentyl alcohol and 10ml ethylene glycol diethyl ether and 20ml water;
C. the sediment after separating is used 60ml tert-pentyl alcohol and 10ml ethylene glycol diethyl ether pulping and washing again, and isolated sediment is under 60 ℃ of temperature, and vacuum drying obtains catalyst B to weight.The analysis showed that this catalyst has following composition: Zn
3[Co (CN)
6]
20.076ZnCl
22.5C
5H
12O1.9C
6H
14O
2
Embodiment 3
A. 4.0g hexacyanocobaltate acid calcium is dissolved in the 120ml deionized water, makes 0.06mol/l hexacyanocobaltate acid calcium solution; The 8.7g zinc nitrate hexahydrate is dissolved in the 20ml deionized water, make the 2.6mol/l zinc nitrate solution, simultaneously the 112ml tert-butyl alcohol, 38ml diethylene glycol dimethyl ether, hexacyanocobaltate acid calcium solution, zinc nitrate solution are added in the reactor and stir generation precipitation, separation; Wherein the addition of material is:
Zn
2+: [Co (CN)
6]
3-=3.6: 1 (mol ratio)
The tert-butyl alcohol: diethylene glycol dimethyl ether=3: 1 (volume ratio)
Every mole of [Co (CN)
6]
3-Add 8.2 liters of organic matters
B. isolated sediment is isolated sediment with the mixture pulping and washing of the 112ml tert-butyl alcohol and 38ml diethylene glycol dimethyl ether and 20ml water;
C. the sediment after separating is used the 112ml tert-butyl alcohol and 38ml diethylene glycol dimethyl ether pulping and washing again, and isolated sediment is under 60 ℃ of temperature, and vacuum drying obtains catalyst C to weight.The analysis showed that this catalyst has following composition: Zn
3[Co (CN)
6]
20.065ZnCl
21.7C
4H
10O2.8C
6H
14O
3
Embodiment 4
A. 6.0g hexacyanocobaltate acid calcium is dissolved in the 50ml deionized water, makes 0.2mol/l hexacyanocobaltate acid calcium solution; The 20.8g zinc nitrate hexahydrate is dissolved in the 20ml deionized water, make the 3.5mol/l zinc nitrate solution, simultaneously 130ml tert-pentyl alcohol, 130ml diethylene glycol diethyl ether, hexacyanocobaltate acid calcium solution, zinc nitrate solution are added in the reactor and stir generation precipitation, separation; Wherein the addition of material is:
Zn
2+: [Co (CN)
6]
3-=3.2: 1 (mol ratio)
Tert-pentyl alcohol: diethylene glycol diethyl ether=1: 1 (volume ratio)
Every mole of [Co (CN)
6]
3-Add 13.0 liters of organic matters
B. isolated sediment is isolated sediment with the mixture pulping and washing of 130ml tert-pentyl alcohol and 130ml diethylene glycol diethyl ether and 20ml water;
C. the sediment after separating is used 130ml tert-pentyl alcohol and 130ml diethylene glycol diethyl ether pulping and washing again, and isolated sediment is under 60 ℃ of temperature, and vacuum drying obtains catalyst D to weight.The analysis showed that this catalyst has following composition: Zn
3[Co (Cn)
6]
20.081ZnCl
20.8C
5H
12O3.0C
8H
18O
3
Embodiment 5
A. 4.8g hexacyanocobaltate acid sodium is dissolved in the 60ml deionized water, makes 0.26mol/l hexacyanocobaltate acid sodium solution; The 9.9g zinc bromide is dissolved in the 20ml deionized water, makes 2.2mol/l zinc bromide solution, stirring in the 20ml tert-butyl alcohol, 80ml dibutyl ethylene glycol ether, hexacyanocobaltate acid sodium solution, the zinc bromide solution adding reactor, generate precipitation simultaneously, separate; Wherein the addition of material is:
Zn
2+: [Co (CN)
6]
3-=2.6: 1 (mol ratio)
The tert-butyl alcohol: dibutyl ethylene glycol ether=1: 4 (volume ratio)
Every mole of [Co (CN)
6]
3-Add 6.2 liters of organic matters
B. isolated sediment is isolated sediment with the mixture pulping and washing of the 20ml tert-butyl alcohol and 80ml dibutyl ethylene glycol ether and 20ml water;
C. the sediment after separating is used the 20ml tert-butyl alcohol and 80ml dibutyl ethylene glycol ether pulping and washing again, and isolated sediment is under 60 ℃ of temperature, and vacuum drying obtains catalyst E to weight.The analysis showed that this catalyst has following composition: Zn
3[Co (CN)
6]
20.052ZnCl
20.6C
4H
10O3.3C
12H
26O
3
Embodiment 6
A. 7.7g hexacyanocobaltate acid sodium is dissolved in the 90ml deionized water, makes 0.3mol/l hexacyanocobaltate acid sodium solution; The 13.5g zinc bromide is dissolved in the 20ml deionized water, makes 3.0mol/l zinc bromide solution, stirring in 50ml tert-pentyl alcohol, 350ml triethylene glycol dimethyl ether, hexacyanocobaltate acid sodium solution, the zinc bromide solution adding reactor, generate precipitation simultaneously, separate; Wherein the addition of material is:
Zn
2+: [Co (CN)
6]
3-=2.2: 1 (mol ratio)
Tert-pentyl alcohol: triethylene glycol dimethyl ether=1: 7 (volume ratio)
Every mole of [Co (CN)
6]
3-Add 14.7 liters of organic matters
B. isolated sediment is isolated sediment with the mixture pulping and washing of 50ml tert-pentyl alcohol and 350ml triethylene glycol dimethyl ether and 20ml water;
C. the sediment after separating is used 50ml tert-pentyl alcohol and 350ml triethylene glycol dimethyl ether pulping and washing again, and isolated sediment is under 60 ℃ of temperature, and vacuum drying obtains catalyst F to weight.The analysis showed that this catalyst has following composition: Zn
3[Co (CN)
6]
20.073ZnCl
20.6C
5H
12O3.7C
8H
18O
4
Embodiment 7
Synthesizing of PPG
Adding 68.6g molecular weight is 700 PPOX triol or polypropylene oxide glycol and 0.164g catalyst in 2 liters of reactors, under agitation be warming up to reaction temperature, after vacuumizing dehydration, add the 10g expoxy propane, when the pressure in the question response device has obvious decline, slowly add expoxy propane, the speed that adds is as the criterion about 40psi with the pressure of keeping in the reactor, the addition of expoxy propane is by the decision of the molecular weight of PPG, after adding, during constant pressure in the question response device, reaction finishes, unreacted expoxy propane vacuumizes and removes, and the product via hole diameter is that 0.45～1.2u filter screen filters under 100 ℃ of temperature, obtains PPG.
The character of reaction temperature, conversion ratio and PPG sees Table 1, and the catalyst remaining quantity in the PPG sees Table 2.
Table 1 catalyst reaction temperatures (℃) conversion ratio (%) hydroxyl value (mgKOH/g) degree of functionality degree of unsaturation (meq/g) A 60＞98 29.8 3 0.0021A 105＞98 30.2 3 0.0028B 105＞98 29.5 3 0.0030B 150＞95 15.8 2 0.0054C 30＞95 28.4 3 0.0018D 80＞98 27.7 3 0.0023E 105＞98 15.6 2 0.0032F 125＞98 30.5 3 0.0036
The remaining cobalt of the remaining zinc of table 2 catalyst hydroxyl value (mgKOH/g) degree of functionality catalyst amount (ppm) (ppm) (ppm) A 29.8 3 200＜5＜2A 30.2 3 100＜4＜2B 29.5 3 200＜5＜2B 15.8 2 100＜4＜2C 28.4 3 100＜4＜2D 27.7 3 100＜4＜2E, 15.6 2 100＜4＜2F 30.5 3 100＜4＜2
Claims (9)
1. DMC catalysts is characterized in that the composed as follows of catalyst:
Zn
3[Co(CN)
6]
2·aZnCl
2·bH
2O·cL·dL′
Wherein L is a kind of organic alcohol, and L ' is a kind of organic ether, and a, b, c, d are coefficients, a=0.05-1.0, b=1.0-2.0, c=0.5-3.0, d=1.0-4.0.
2. a kind of DMC catalysts according to claim 1 is characterized in that described organic alcohol is the organic alcohol with C4-C10 of tertiary alcohol structure.
3. a kind of DMC catalysts according to claim 1 is characterized in that described organic alcohol is the tert-butyl alcohol or tert-pentyl alcohol.
4. a kind of DMC catalysts according to claim 1 is characterized in that described organic ether is the organic ether that contains 2-6 ether oxygens key.
5. a kind of DMC catalysts according to claim 1 is characterized in that described organic ether is glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether or triethylene glycol dimethyl ether.
6. the preparation method of a DMC catalysts is characterized in that following steps:
A. rare aqueous solution of the hexacyanocobaltate acid salt of the aqueous solution of dense zinc salt, alkali metal or alkaline-earth metal, alcohol, ether are added in the reactor simultaneously, stir, generate precipitation, separate; Wherein the addition of material is:
Zn
2+: [Co (CN)
6]
3-=(2-5): 1 (mol ratio)
Alcohol: ether=(0.1-10): 1 (volume ratio)
Every mole of [Co (CN)
6]
3-Add organic matter 4-15 liter
B. isolated sediment use with (a) step in form the organic matter of isodose mutually and equal the mixture that organic matter adds 1/15～1/4 water of volume and carry out pulping and washing, isolate sediment,
C. the sediment after separating use again with (a) step in form mutually that the organic matter of isodose carries out pulping and washing, isolate sediment under 60 ℃ of temperature, vacuum drying obtains catalyst to constant weight.
7. the preparation method of a kind of DMC catalysts according to claim 6 is characterized in that described zinc salt is an inorganic zinc salt.
8. the preparation method of a kind of DMC catalysts according to claim 6 is characterized in that described zinc salt is zinc chloride, zinc bromide, zinc nitrate or zinc sulfate.
9. the preparation method of a kind of DMC catalysts according to claim 6 is characterized in that described hexacyanocobaltate acid salt is Cobalt Potassium Cyanide or hexacyanocobaltate acid sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98108166A CN1080590C (en) | 1998-04-29 | 1998-04-29 | Double metal cyanide catalyst and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98108166A CN1080590C (en) | 1998-04-29 | 1998-04-29 | Double metal cyanide catalyst and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1233530A CN1233530A (en) | 1999-11-03 |
| CN1080590C true CN1080590C (en) | 2002-03-13 |
Family
ID=5219550
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98108166A Expired - Fee Related CN1080590C (en) | 1998-04-29 | 1998-04-29 | Double metal cyanide catalyst and its prepn. method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1080590C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085829B (en) * | 2007-06-22 | 2010-06-02 | 广西壮族自治区化工研究院 | Catalyst for synthesizing polyether glycol from sucrose and oxidized olefin and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04284850A (en) * | 1991-03-13 | 1992-10-09 | Asahi Glass Co Ltd | Production of composite metal cyanide complex catalyst |
| CN1140181A (en) * | 1995-05-15 | 1997-01-15 | 阿克奥化学技术有限公司 | Highly active double metal cyanide complex catalysts |
| CN1145373A (en) * | 1995-08-22 | 1997-03-19 | 阿科化学技术公司 | Improved polyether-containing double metal cyanide catalysts |
| CN1147423A (en) * | 1995-07-24 | 1997-04-16 | 阿科化学技术公司 | Highly active double metal cyanide complex catalysts |
| JP4145123B2 (en) * | 2002-11-18 | 2008-09-03 | 株式会社オンダ製作所 | Fitting |
-
1998
- 1998-04-29 CN CN98108166A patent/CN1080590C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04284850A (en) * | 1991-03-13 | 1992-10-09 | Asahi Glass Co Ltd | Production of composite metal cyanide complex catalyst |
| CN1140181A (en) * | 1995-05-15 | 1997-01-15 | 阿克奥化学技术有限公司 | Highly active double metal cyanide complex catalysts |
| CN1147423A (en) * | 1995-07-24 | 1997-04-16 | 阿科化学技术公司 | Highly active double metal cyanide complex catalysts |
| CN1145373A (en) * | 1995-08-22 | 1997-03-19 | 阿科化学技术公司 | Improved polyether-containing double metal cyanide catalysts |
| JP4145123B2 (en) * | 2002-11-18 | 2008-09-03 | 株式会社オンダ製作所 | Fitting |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085829B (en) * | 2007-06-22 | 2010-06-02 | 广西壮族自治区化工研究院 | Catalyst for synthesizing polyether glycol from sucrose and oxidized olefin and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1233530A (en) | 1999-11-03 |
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